CN101962459B - Flame retardant composite material with high flow and preparation method - Google Patents
Flame retardant composite material with high flow and preparation method Download PDFInfo
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- CN101962459B CN101962459B CN2010105155547A CN201010515554A CN101962459B CN 101962459 B CN101962459 B CN 101962459B CN 2010105155547 A CN2010105155547 A CN 2010105155547A CN 201010515554 A CN201010515554 A CN 201010515554A CN 101962459 B CN101962459 B CN 101962459B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention provides a flame retardant composite material with high flow and a preparation method. The invention aims to improve the machining performance of the composite material, so that the composite material has the high tenacity, high environmental-friendly flame retardance and high flow. The invention adopts the technical scheme that the composite material comprises the following components in part by mass: 60 to 70 parts of polrvinyl chloride, 20 to 30 parts of butadiene-acrylonitrile-styrene, 1 to 5 parts of styrene-butadiene-styrene, 1 to 3 parts of chlorinated polyethylene, 1.0 to 2.0 parts of heat stabilizer, 5 to 8 parts of plasticizer, 0.5 to 1.5 parts of lubricating agent, 0.5 to 1.0 part of PVC self-plasticizer and 0.3 to 0.5 part of intensifier. A small amount of chemically-modified PVC self-plasticizer is added into the composite material, so the machining performance of the composite material is improved, the plasticizing degree and mechanical property of the material are improved, and the self-plastification effect of the material is realized.
Description
Technical field
The present invention relates to material, specifically, relate to a kind of flame retardant composite material with high flow and preparation method thereof.
Background technology
China is starting late aspect the flame-retardant ABS compound material development.About the nineties in 20th century, R﹠D institution, universities and colleges and the ABS manufacturers such as China Shanghai Gaoqiao petro-chemical corporation, Qingtao Chemical Engineering College, Guangzhou Synthetic Materials Inst all carried out research and development, but its main exploitation content is that flame retardant resistance, thermostability, the raising physical and mechanical properties for flame-proof ABS adopts aspects such as adding the 3rd unit polymer modification to carry out.Although above-mentioned research obtains some progress at aspects such as flame retardant resistance and thermostabilitys, but and the contradiction between unresolved such Material Physics mechanical property and the moulding processability, and the product of development is larger to the corrodibility of processing units, has limited applying of this series products; Simultaneously, flame-retardant system also adopt that bromide fire retardants and antimonous oxide cooperate the halogen flame-retardant system arranged, when burning, can decomposite corrosive bromize hydrogen gas, to human body and environment.
Recently the average annual growth rate of demand of more than ten years world's polyblend is about 10%, and the alloy of general-purpose plastics and engineering plastics wherein, more becomes the focus kind of each major company's active development.
The ABS/PVC alloy has higher shock strength and preferably thermostability, flame retardant resistance and comparatively ideal cost/performance index, development along with science and technology, people are more and more higher to the performance requriements of material, the defective of ABS/PVC alloy itself, as: flexural strength is not too high, heat-drawn wire is low, outward appearance is not ideal enough, processing fluidity is poor etc. has limited its development.As seen, the existing problems of prior art are that processing characteristics, toughness and flowability still have some deficits.
Summary of the invention
The invention provides a kind of flame retardant composite material with high flow and preparation method, the objective of the invention is to improve Drawing abillity, make material have high tenacity, environmental protection flame retardant and high workability.
In order to reach the purpose that solves the prior art problem, technical scheme of the present invention is a kind of flame retardant composite material with high flow, it is characterized in that: described matrix material comprises following component, in mass fraction, and polyvinyl chloride 60-70 part, acrylonitrile-butadiene-styrene (ABS) 20-30 part, styrene-butadiene-styrene 1-5 part, chlorinatedpolyethylene 1-3 part, thermo-stabilizer 1.0-2.0 part, softening agent 5-8 part, lubricant 0.5-1.5 part, PVC self-plasticization agent 0.5-1.0 part, toughener 0.3-0.5 part.
The agent of described PVC self-plasticization is MC100 or crystallite PVC powder.
Described thermo-stabilizer is one or more in organotin stabilizer DMTTG, organotin stabilizer DOTTG, organo-tin het stabilizer DOTL or the two single-ethylhexyl maleate dioctyltin.
Described softening agent is one or more among terephthalic acid di-isooctyl, 1,2-cyclohexane dicarboxylic acid diisopropyl ester or the UN488.
Described lubricant is one or more among stearic acid, barium stearate, calcium stearate, E wax, YG-16, PE wax or the EBS.
Described toughener is PA20 or CaCO
3In one or more.
A kind of preparation method of flame retardant composite material with high flow, described method is carried out according to following step:
(1) first acrylonitrile-butadiene-styrene (ABS) is carried out drying in 95-105 ℃ of scope;
(2) polyvinyl chloride, chlorinatedpolyethylene, thermo-stabilizer, the agent of PVC self-plasticization, lubricant, softening agent and toughener umber is in accordance with regulations added high mixer, mixed 8-12 minute, when temperature is elevated to 45-55 ℃, stop to mix;
(3), when the component drop in temperature of step (2) during to 28-32 ℃, add again styrene-butadiene-styrene and the dried acrylonitrile-butadiene-styrene (ABS) of regulation umber, temperature is controlled at 78-82 ℃, start mixes discharging in 3-8 minute again;
(4), with in the step (3) just mixed component join in the twin screw extruder, forcing machine respectively the section of heating temperature range between 140-170 ℃, after extruding through the tank cool to room temperature, by the dicing machine granulation.
Purpose of the present invention adopts New Compatilizer to improve the consistency of ABS and PVC, and the adjacent benzene class softening agent of abandoning tradition improves Drawing abillity, makes material have high tenacity, environmental protection flame retardant and high workability.
The present invention forms alloy with ABS and PVC, can reduce on the one hand ABS cost, realize the fire-retardant of ABS, can improve the processing characteristics of PVC simultaneously, realize having complementary advantages.Can make novel flame-proof ABS modifying material.The ABS/PVC alloy has good flame retardant resistance and toughness.PVC provides extreme ultraviolet stability and inherent flame retardant resistance, and ABS has brought good shock resistance and workability energy.This flame retardant products has good processing fluidity and flame retardant properties can reach the V0 level.
The present invention improves the over-all properties of ABS/PVC alloy in order to overcome the problem of prior art, is necessary the ABS/PVC alloy is carried out modification.By blend technique and change ABS and the proportioning of PVC, adjust plasticizer loading among the PVC, under the conditions such as high temperature, high-shear, form the tertiary blending system.
The technical characterstic of matrix material maximum of the present invention is to have used power chemotype processing aid MC100, not only increased the consistency between ABS resin and the polyvinyl chloride resin, simultaneously, utilize the self-plasticization of MC100, greatly increase this novel flame-retardant ABS matrix material mobile bad defective in the course of processing, reduced simultaneously the processing temperature of this novel flame-retardant ABS matrix material, avoided also having avoided the corrosion to processing units because of the impact of PVC degraded on the performance of matrix material.The self-plasticization principle of MC100 is: utilize force-chemical reaction to eliminate and be unfavorable for multi-level pomegranate structure and the microlitic structure that PVC processes, make the PVC agglomerated particles in the course of processing, be easy to plastify into the molecular melt that line style flows, understand recrystallize when molecular melt is cooled to solidify from molten state and do not reduce intermolecular interaction, caused under the prerequisite that does not reduce its mechanical property, having solved its difficult processing problems.Adding is a small amount of in this novel flame-retardant ABS matrix material can improve the processing characteristics of this matrix material through the PVC of power chemical modification self-plasticization properties-correcting agent MC100, has improved degree of plasticification and mechanical property, realizes the self-plasticization effect.And after the machine-shaping, the matrix material intramolecular crystallization of reuniting has become the intermolecular crystallization of welding, has played the effect of " Tie molecule ", has improved the mechanical property of matrix material.
Description of drawings
Fig. 1 is a kind of flame retardant composite material with high flow Production Flow Chart of the present invention synoptic diagram.
Embodiment
Embodiment 1, unit: Kg
65 parts of polyvinyl chloride, 25 parts of acrylonitrile-butadiene-styrene (ABS)s, 2 parts of styrene-butadiene-styrenes, 1 part of chlorinatedpolyethylene, organotin stabilizer DMTTG1.4 part, 6 parts of terephthalic acid di-isooctyls, 1.0 parts of stearic acid, 0.6 part of PVC self-plasticization agent MC100, PA-200.3 part.
Embodiment 2 units: Kg
60 parts of polyvinyl chloride, 30 parts of acrylonitrile-butadiene-styrene (ABS)s, 2 parts of styrene-butadiene-styrenes, 1.5 parts of chlorinatedpolyethylenees, organotin stabilizer D0TTG1.3 part, 1,5.5 parts of 2-cyclohexane dicarboxylic acid diisopropyl esters, 1.0 parts of barium stearates, 0.7 part of PVC self-plasticization agent MC100,0.3 part of PA-20.
Embodiment 3 units: Kg
70 parts of polyvinyl chloride, 20 parts of acrylonitrile-butadiene-styrene (ABS)s, 5 parts of styrene-butadiene-styrenes, 1 part of chlorinatedpolyethylene, organotin stabilizer DMTTG1.4 part, 6.8 parts of terephthalic acid di-isooctyls, 1.0 parts of calcium stearates, 0.8 part of PVC self-plasticization agent MC100,0.3 part of PA-20.
Embodiment 4 units: Kg
65 parts of polyvinyl chloride, 30 parts of acrylonitrile-butadiene-styrene (ABS)s, 2 parts of styrene-butadiene-styrenes, 3 parts of chlorinatedpolyethylenees, organotin stabilizer DMTTG1.4 part, 4 parts of terephthalic acid di-isooctyls, YG-161.1 part, 0.5 part of PVC self-plasticization agent MC100,0.3 part of PA-20.
Embodiment 5 units: Kg
65 parts of polyvinyl chloride, 25 parts of acrylonitrile-butadiene-styrene (ABS)s, 1.2 parts of styrene-butadiene-styrenes, 3 parts of chlorinatedpolyethylenees, 1.4 parts of two single-ethylhexyl maleate dioctyltins, 1,5 parts of 2-cyclohexane dicarboxylic acid diisopropyl esters, 0.8 part of stearic acid, 0.8 part of PVC self-plasticization agent MC100,0.3 part of PA-20.
Embodiment 6 units: Kg
66 parts of polyvinyl chloride, 25 parts of acrylonitrile-butadiene-styrene (ABS)s, 3 parts of styrene-butadiene-styrenes, 3 parts of chlorinatedpolyethylenees, 1.6 parts of two single-ethylhexyl maleate dioctyltins, 3 parts of UN488,1.0 parts in E wax, 0.6 part of PVC self-plasticization agent MC100, CaCO
30.5 part.
Referring to Fig. 1, the preparation method of above-described embodiment carries out according to following step:
(1) first acrylonitrile-butadiene-styrene (ABS) is carried out drying in 95-105 ℃ of scope;
(2) polyvinyl chloride, chlorinatedpolyethylene, thermo-stabilizer, the agent of PVC self-plasticization, lubricant, softening agent and toughener umber is in accordance with regulations added high mixer, mixed 8-12 minute, when temperature is elevated to 45-55 ℃, stop to mix;
(3), when the component drop in temperature of step (2) during to 28-32 ℃, add again styrene-butadiene-styrene and the dried acrylonitrile-butadiene-styrene (ABS) of regulation umber, temperature is controlled at 78-82 ℃, start mixes discharging in 3-8 minute again;
(4), with in the step (3) just mixed component join in the twin screw extruder, forcing machine respectively the section of heating temperature range between 140-170 ℃, after extruding through the tank cool to room temperature, by the dicing machine granulation.
The performance test of above-described embodiment is as follows:
Relevant test method and standard:
1 flowability (melting index) and mechanical property adopt the ASTM standard.
2 flame retardant resistances adopt the UL-94 touchstone.
More than test shows that the flowability of matrix material of the present invention has reached higher index, and has high flame resistance.
PVC/ABS alloy composite materials of the present invention can directly be made finished product by Shooting Technique.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (6)
1. flame retardant composite material with high flow, it is characterized in that: described matrix material comprises following component, in mass fraction, and polyvinyl chloride 60-70 part, acrylonitrile-butadiene-styrene (ABS) 20-30 part, styrene-butadiene-styrene 1-5 part, chlorinatedpolyethylene 1-3 part, thermo-stabilizer 1.0-2.0 part, softening agent 5-8 part, lubricant 0.5-1.5 part, PVC self-plasticization agent MC1000.5-1.0 part, toughener 0.3-0.5 part.
2. a kind of flame retardant composite material with high flow according to claim 1, it is characterized in that: described thermo-stabilizer is one or more in organotin stabilizer DMTTG, organotin stabilizer DOTTG, organo-tin het stabilizer DOTL or the two single-ethylhexyl maleate dioctyltin.
3. a kind of flame retardant composite material with high flow according to claim 2, it is characterized in that: described softening agent is one or more among terephthalic acid di-isooctyl, 1,2-cyclohexane dicarboxylic acid diisopropyl ester or the UN488.
4. a kind of flame retardant composite material with high flow according to claim 3, it is characterized in that: described lubricant is one or more among stearic acid, barium stearate, calcium stearate, YG-16, PE wax or the EBS.
5. a kind of flame retardant composite material with high flow according to claim 4, it is characterized in that: described toughener is PA20 or CaCO
3In one or more.
6. the preparation method of claim 1 flame retardant composite material with high flow is characterized in that, described method is carried out according to following step:
(1) first acrylonitrile-butadiene-styrene (ABS) is carried out drying in 95-105 ℃ of scope;
(2) polyvinyl chloride, chlorinatedpolyethylene, thermo-stabilizer, PVC self-plasticization agent MC100, lubricant, softening agent and toughener umber is in accordance with regulations added high mixer, mixed 8-12 minute, when temperature is elevated to 45-55 ℃, stop to mix;
(3), when the component drop in temperature of step (2) during to 28-32 ℃, add again styrene-butadiene-styrene and the dried acrylonitrile-butadiene-styrene (ABS) of regulation umber, temperature is controlled at 78-82 ℃, start mixes discharging in 3-8 minute again;
(4), with in the step (3) just mixed component join in the twin screw extruder, forcing machine respectively the section of heating temperature range between 140-170 ℃, after extruding through the tank cool to room temperature, by the dicing machine granulation.
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| CN2010105155547A CN101962459B (en) | 2010-10-22 | 2010-10-22 | Flame retardant composite material with high flow and preparation method |
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| CN101962459B true CN101962459B (en) | 2013-04-03 |
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| CN104109304B (en) * | 2014-06-23 | 2016-08-24 | 安徽荣玖光纤通信科技有限公司 | A kind of high flowing polyvinyl chloride cable material and preparation method thereof |
| CN104262799B (en) * | 2014-10-23 | 2016-07-06 | 山东省农业科学院家禽研究所 | The Plastic wrapper that a kind of wearability is high |
| CN112662094B (en) * | 2020-12-31 | 2022-09-27 | 浙江威思康塑胶有限公司 | Flame-retardant high-elasticity PVC injection molding material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111882A (en) * | 1976-09-17 | 1978-09-05 | Stauffer Chemical Company | Flame retardant plasticizer formulation for polyvinyl chloride containing dimethyl methylphosphonate for haze reduction |
| CN1133872A (en) * | 1996-03-06 | 1996-10-23 | 生寿斋 | Composition for antistatic fire-proof plastic pipe for coal mine |
| CN101735531A (en) * | 2009-11-19 | 2010-06-16 | 生寿斋 | Mining metal/polymer composite conveyor track supporting roller and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010024512A (en) * | 1997-10-16 | 2001-03-26 | 데이비드 디. 샌더스 | Polyvinyl chloride based plenum cable compositions |
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2010
- 2010-10-22 CN CN2010105155547A patent/CN101962459B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111882A (en) * | 1976-09-17 | 1978-09-05 | Stauffer Chemical Company | Flame retardant plasticizer formulation for polyvinyl chloride containing dimethyl methylphosphonate for haze reduction |
| CN1133872A (en) * | 1996-03-06 | 1996-10-23 | 生寿斋 | Composition for antistatic fire-proof plastic pipe for coal mine |
| CN101735531A (en) * | 2009-11-19 | 2010-06-16 | 生寿斋 | Mining metal/polymer composite conveyor track supporting roller and manufacturing method thereof |
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