CN102153743A - Preparation method of self-lubricating and high-strength pouring nylon - Google Patents
Preparation method of self-lubricating and high-strength pouring nylon Download PDFInfo
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- CN102153743A CN102153743A CN 201110009588 CN201110009588A CN102153743A CN 102153743 A CN102153743 A CN 102153743A CN 201110009588 CN201110009588 CN 201110009588 CN 201110009588 A CN201110009588 A CN 201110009588A CN 102153743 A CN102153743 A CN 102153743A
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Abstract
The invention relates to a preparation method of a self-lubricating and high-strength pouring nylon, comprising the following steps of: (1) stirring and heating a caprolactam monomer, surface-modified nano TiO2 and nano graphite powder subjected to alkaline treatment, and vacuumizing simultaneously, continuously stirring a caprolactam fused mass mixture to obtain a caprolactam fused mass containing a nano composite material; (2) adding a sodium hydroxide solid to the caprolactam fused mass, raising temperature and continuously stirring to obtain an alkaline caprolactam fused mass mixture; (3) restoring the pressure of a reaction kettle to the atmospheric pressure, adding IPDI (Isophorone Diisocyanate) or TDI (Toluene Diisocynate) to the reaction kettle, uniformly stirring to obtain a caprolactam nylon prepolymer; and (4) flowing or pressurizing the prepolymer and injecting to a mold cavity, closing a mold, then continuously warming, then naturally cooling to room temperature to obtain a formed self-lubricating and high-strength pouring nylon part. The preparation method of the self-lubricating and high-strength pouring nylon has the advantages of simple process device and apparatus, simple process route, simple formation and control and unlimited part size and shape.
Description
Technical field
The present invention relates to a kind of preparation method of self-lubricating high strength cast nylon, belong to macromolecule nylon material technology field.
Background technology
Cast nylon is that a kind of density is little, mechanical strength is high, toughness is high, excellent electrical properties, wear-resisting, antidetonation sound-absorbing, acid and alkali-resistance and common organic solvents, be easy to the macromolecular structure material of forming process, the wear parts that can be widely used in mechanical means, Alloy instead of Copper and alloy are as the wear-resisting consumable accessory of equipment.As axle sleeve, bearing shell, lining, liner plate, gear, piston ring, sealing-ring, slide block, ball bowl, impeller, blade, cam, nut, valve block, pipeline, stuffing box, tooth bar, belt pulley and pump rotor etc.Use cast nylon component, can not only improve mechanical efficiency, reduce maintenance, and can prolong more than two times work-ing life.But with the metallographic phase ratio, cast nylon exists intensity, modulus and heat-drawn wire lower, and poor dimensional stability to shortcomings such as notch shock sensitivities, thereby limits the scope of its application.So be necessary cast nylon is carried out modification, improve its over-all properties.
The preparation technology who pours into a mould nylon material now both at home and abroad mainly is pure nylon or the modified nylon materials that adds inorganic powder.Though have above-mentioned advantage as cast nylon, be difficult to solve simultaneously for the problem of intensity and wear resistance.Improve the intensity of cast nylon material, the research and the preparation that particularly have the structural timber of self-lubricating ability still have very big demand, have vast market prospect.
Summary of the invention
Problem to be solved by this invention is to propose a kind of self-lubricating high strength cast nylon preparation method at above-mentioned prior art, adopt caprolactam monomer and the modified Nano material is compound makes the nylon performed polymer through base catalysis under the vacuum anhydrous condition, and directly casting obtains self-lubricating high strength cast nylon parts, the cast nylon parts that obtain, frictional coefficient is little, can solve the high-wear resistance of the parts of nylon; Because of the intensity height, range of application is wider simultaneously.
The present invention solves the problems of the technologies described above the solution that is adopted to be: the preparation method of self-lubricating high strength cast nylon is characterized in that including following steps:
1) gets the caprolactam monomer of 1000 parts of mass fractions, the nano-TiO that the surface modification of mass fraction 1-20 part is crossed
2The Nano graphite powder of crossing with the basic treatment of mass fraction 1-50 part, join in the reactor, stirring also heats to 120 ℃-140 ℃, vacuumize simultaneously, make the reactor internal gas pressure be lower than 500Pa, continue to stir the hexanolactam melted blend 20-60 minute, obtain containing the hexanolactam melt of nano composite material;
2) sodium hydrate solid of massfraction 2-8 part is joined in the hexanolactam melt that contains nano composite material that step 1) obtains, keep the reactor internal gas pressure to be lower than 500Pa, be warmed up to 140-150 ℃, continue to stir 20-60 minute, obtain the alkaline caprolactam melted blend;
3) logical nitrogen recovers reactor pressure to normal atmosphere in reactor, under the violent stirring condition with the 3-isocyanic ester methylene-3 of massfraction 2-8 part, 5,5-3-methyl cyclohexanol based isocyanate (IPDI) or tolylene diisocyanate (TDI) join step 2) in the alkaline caprolactam melted blend of gained, stir, be warming up to 140-155 ℃ simultaneously, obtain hexanolactam nylon performed polymer;
4) casting mold is preheating to 165-190 ℃ and constant temperature in heating container, gravity flow of hexanolactam nylon performed polymer or pressurization that step 3) obtains are injected in the mold cavity, the follow-up continuation of insurance temperature of close die 10-120 minute, naturally cool to room temperature then, promptly obtain the self-lubricating high strength cast nylon parts of forming.
Press such scheme, described nano-TiO
2Surface modifying treatment be: with nano-TiO
2Join in the dehydrated alcohol, stir fast, obtain TiO
2The dehydrated alcohol mixture; Getting KH-550 or KH-50 coupling agent is dissolved in the less water and and TiO
2The dehydrated alcohol mixture mix, stirred 4-6 hour at 40-60 ℃, the system centrifugation obtains lower floor's paste, puts into baking oven 80-100 ℃ dry for standby.
Press such scheme, the basic treatment method of described Nano graphite powder is: with the technical grade Nano graphite powder in the sodium hydroxide solution of mass percent concentration 10-30%, 20-70 ℃ was soaked down after 12-24 hour, filtered, and the Nano graphite powder that obtains is 100-150 ℃ of dry for standby in baking oven.
Reaction principle of the present invention is as follows:
(1) sodium hydroxide becomes negative ion with the initiation hexanolactam
(2) IPDI or TDI promoting agent and hexanolactam form imide structure
(3) imide structure transfer reaction
The characteristics of self-lubricating high strength cast nylon of comparing the present invention preparation with existing cast nylon are as follows:
It is low that the cast nylon of the present invention preparation has a frictional coefficient, and inner nano-graphite self-lubricating need not to add lubricant as moving parts, has self-lubricating function.By the intensity of nano-material surface effect and coupling effect raising nylon, to compare with ultimate compression strength, the tensile strength of common nylon, intensity has improved more than 20%, and frictional coefficient has reduced more than 60%.
The self-lubricating high strength cast nylon the key technical indexes of the present invention's preparation is as follows:
1. density 1.12-1.2g/cm
3
2. ultimate compression strength: 110-130MPa
3. tensile strength: 85-105MPa
4. elongation at break: 25-30%
5. flexural strength: 100-110MPa
6. shock strength: 6.5-8.5kJ/m
2
7. frictional coefficient: 0.1-0.12
Self-lubricating high strength of the present invention cast nylon preparation method has that process unit equipment is simple, and operational path is simple and direct, and moulding control is simple, part dimension, the unconfined advantage of shape.
Embodiment
Following for embodiment will help to understand the present invention:
Embodiment 1:
With the 20g nano-TiO
2Join in the 80ml dehydrated alcohol, stir fast, obtain TiO
2The dehydrated alcohol mixture; Getting 1g KH-550 coupling agent is dissolved in the 20ml water and and TiO
2The dehydrated alcohol mixture mix, stirred 4 hours at 60 ℃, the system centrifugation obtains lower floor's paste, puts into 90 ℃ of oven dry of baking oven, grinds 400 mesh sieves, obtains the nano-TiO that surface modification is crossed
2
Embodiment 2:
With the 100g nano-TiO
2Join in the 500ml dehydrated alcohol, stir fast, obtain TiO
2The dehydrated alcohol mixture; Getting 4g KH-50 coupling agent is dissolved in the 50ml water and and TiO
2The dehydrated alcohol mixture mix, stirred 6 hours at 50 ℃, the system centrifugation obtains lower floor's paste, puts into 100 ℃ of oven dry of baking oven, grinds 400 mesh sieves, obtains the nano-TiO that surface modification is crossed
2
Embodiment 3:
With 20g technical grade Nano graphite powder in the sodium hydroxide solution that joins 200ml mass percent concentration 30%, after soaking 12 hours under 50 ℃, remove by filter sodium hydroxide solution, Nano graphite powder after filtering is put into 110 ℃ of oven dry of baking oven, grind 400 mesh sieves, obtained the alkaline nano Graphite Powder 99.
Embodiment 4:
With 100g technical grade Nano graphite powder in the sodium hydroxide solution that joins 900ml mass percent concentration 10%, after soaking 24 hours under 60 ℃, remove by filter sodium hydroxide solution, Nano graphite powder after filtering is put into 110 ℃ of oven dry of baking oven, grind 400 mesh sieves, obtained the alkaline nano Graphite Powder 99.
Embodiment 5:
(1) gets the first grade hexanolactam of 500g and the nano-TiO that 2g crosses through surface modification
2The Nano graphite powder that (embodiment 1) and 2g cross through basic treatment (embodiment 3) mixes, join in the reactor, stirring also heats to 130 ℃, bleed with vacuum pump, making the reactor internal gas pressure is 100Pa, remove the moisture in the raw material, continue to stir the hexanolactam melted blend 40 minutes, obtain containing the hexanolactam melt of nano composite material;
(2) sodium hydrate solid of 1.5g is joined in the hexanolactam melt that contains nano composite material that step 1) obtains, and maintenance reactor internal gas pressure is 100Pa, be warmed up to 145 ℃, continue to stir 30 minutes, basic catalyst is dissolved in the hexanolactam, and the moisture of reaction is removed, obtain the alkaline caprolactam melted blend;
(3) logical nitrogen is in reactor, be elevated to normal atmosphere until reactor pressure, under the violent stirring condition with the 3-isocyanic ester methylene-3 of 1.5g, 5,5-3-methyl cyclohexanol based isocyanate (IPDI) joins in the above-mentioned alkaline caprolactam melted blend, stir, be warming up to 150 ℃ simultaneously, obtain pouring into a mould the hexanolactam nylon performed polymer of nylon;
(4) will pour into a mould with mould and be placed in the heating container, be preheating to 170 ℃ and constant temperature more than 10 minutes, hexanolactam nylon performed polymer is injected in the mold cavity by gravity flow or pressurization, the follow-up continuation of insurance temperature of close die 40 minutes, naturally cool to room temperature then, promptly obtain self-lubricating high strength cast nylon parts.
The self-lubricating high strength cast nylon of present embodiment 5 preparations is compared with the common cast nylon that does not contain nano composite material, and the main raw performance data is as follows:
| Material property | Unit | Common cast nylon | This routine self-lubricating high strength cast nylon |
| Density | g/cm 3 | 1.15 | 1.16 |
| Tensile strength | MPa | 85 | 105 |
| Elongation at break | ％ | 40 | 30 |
| Flexural strength | MPa | 90 | 105 |
| Ultimate compression strength | MPa | 95 | 120 |
| Shock strength (breach) | KJ/m 2 | 6.0 | 7.0 |
| Shao Shi D hardness | 80-85 | 85-90 | |
| Frictional coefficient | μ | 0.4 | 0.11 |
Embodiment 6:
(1) gets the first grade hexanolactam of 500g and the nano-TiO that 10g crosses through surface modification
2The Nano graphite powder that (embodiment 1) and 10g cross through basic treatment (embodiment 3) mixes, join in the reactor, stirring also heats to 125 ℃, bleed with vacuum pump, making the reactor internal gas pressure is 80Pa, remove the moisture in the raw material, continue to stir the hexanolactam melted blend 30 minutes, obtain containing the hexanolactam melt of nano composite material;
(2) sodium hydrate solid of 3.5g is joined in the hexanolactam melt that contains nano composite material that step 1) obtains, and maintenance reactor internal gas pressure is 80Pa, be warmed up to 150 ℃, continue to stir 40 minutes, basic catalyst is dissolved in the hexanolactam, and the moisture of reaction is removed, obtain the alkaline caprolactam melted blend;
(3) logical nitrogen is in reactor, be elevated to normal atmosphere until reactor pressure, under the violent stirring condition with the 3-isocyanic ester methylene-3 of 2.5g, 5,5-3-methyl cyclohexanol based isocyanate (IPDI) joins in the above-mentioned alkaline caprolactam melted blend, stir, be warming up to 150 ℃ simultaneously, obtain pouring into a mould the hexanolactam nylon performed polymer of nylon;
(4) will pour into a mould with mould and be placed in the heating container, be preheating to 170 ℃ and constant temperature more than 15 minutes, hexanolactam nylon performed polymer is injected in the mold cavity by gravity flow or pressurization, the follow-up continuation of insurance temperature of close die 100 minutes, naturally cool to room temperature then, promptly obtain self-lubricating high strength cast nylon parts.
Embodiment 7:
(1) gets the first grade hexanolactam of 1000g and the nano-TiO that 12g crosses through surface modification
2The Nano graphite powder that (embodiment 1) and 10g cross through basic treatment (embodiment 3) mixes, join in the reactor, stirring also heats to 130 ℃, bleed with vacuum pump, making the reactor internal gas pressure is 400Pa, remove the moisture in the raw material, continue to stir the hexanolactam melted blend 50 minutes, obtain containing the hexanolactam melt of nano composite material;
(2) sodium hydrate solid of 4g is joined in the hexanolactam melt that contains nano composite material that step 1) obtains, and maintenance reactor internal gas pressure is 400Pa, be warmed up to 145 ℃, continue to stir 30 minutes, basic catalyst is dissolved in the hexanolactam, and the moisture of reaction is removed, obtain the alkaline caprolactam melted blend;
(3) logical nitrogen is in reactor, be elevated to normal atmosphere until reactor pressure, tolylene diisocyanate (TDI) with 6g under the violent stirring condition joins in the above-mentioned alkaline caprolactam melted blend, stir, be warming up to 150 ℃ simultaneously, obtain pouring into a mould the hexanolactam nylon performed polymer of nylon;
(4) will pour into a mould with mould and be placed in the heating container, be preheating to 165 ℃ and constant temperature more than 25 minutes, hexanolactam nylon performed polymer is injected in the mold cavity by gravity flow or pressurization, the follow-up continuation of insurance temperature of close die 30 minutes, naturally cool to room temperature then, promptly obtain self-lubricating high strength cast nylon parts.
Embodiment 8:
(1) gets the first grade hexanolactam of 500Kg and the nano-TiO that 8Kg crosses through surface modification
2The Nano graphite powder that (embodiment 2) and 8Kg cross through basic treatment (embodiment 4) mixes, join in the reactor, stirring also heats to 125 ℃, bleed with vacuum pump, making the reactor internal gas pressure is 80Pa, remove the moisture in the raw material, continue to stir the hexanolactam melted blend 50 minutes, obtain containing the hexanolactam melt of nano composite material;
(2) sodium hydrate solid of 4Kg is joined in the hexanolactam melt that contains nano composite material that step 1) obtains, and maintenance reactor internal gas pressure is 80Pa, be warmed up to 145 ℃, continue to stir 30 minutes, basic catalyst is dissolved in the hexanolactam, and the moisture of reaction is removed, obtain the alkaline caprolactam melted blend;
(3) logical nitrogen is in reactor, be elevated to normal atmosphere until reactor pressure, under the violent stirring condition with the 3-isocyanic ester methylene-3 of 2.5Kg, 5,5-3-methyl cyclohexanol based isocyanate (IPDI) joins in the above-mentioned alkaline caprolactam melted blend, stir, be warming up to 150 ℃ simultaneously, obtain pouring into a mould the hexanolactam nylon performed polymer of nylon;
(4) will pour into a mould with mould and be placed in the heating container, be preheating to 175 ℃ and constant temperature more than 30 minutes, hexanolactam nylon performed polymer is injected in the mold cavity by gravity flow or pressurization, the follow-up continuation of insurance temperature of close die 120 minutes, naturally cool to room temperature then, promptly obtain self-lubricating high strength cast nylon parts.
Embodiment 9:
(1) gets the first grade hexanolactam of 100Kg and the nano-TiO that 1.4Kg crosses through surface modification
2The Nano graphite powder that (embodiment 2) and 1.5Kg cross through basic treatment (embodiment 4) mixes, join in the reactor, stirring also heats to 125 ℃, bleed with vacuum pump, making the reactor internal gas pressure is 80Pa, remove the moisture in the raw material, continue to stir the hexanolactam melted blend 60 minutes, obtain containing the hexanolactam melt of nano composite material;
(2) sodium hydrate solid of 0.25Kg is joined in the hexanolactam melt that contains nano composite material that step 1) obtains, and maintenance reactor air pressure is 80Pa, be warmed up to 145 ℃, continue to stir 40 minutes, basic catalyst is dissolved in the hexanolactam, and the moisture of reaction is removed, obtain the alkaline caprolactam melted blend;
(3) logical nitrogen is in reactor, be elevated to normal atmosphere until reactor pressure, tolylene diisocyanate (TDI) with 0.3Kg under the violent stirring condition joins in the above-mentioned alkaline caprolactam melted blend, stir, be warming up to simultaneously below 150 ℃, obtain pouring into a mould the hexanolactam nylon performed polymer of nylon;
(4) will pour into a mould with mould and be placed in the heating container, and be preheating to 175 ℃ and constant temperature more than 30 minutes, hexanolactam nylon performed polymer is injected in the mold cavity by gravity flow or pressurization, the follow-up continuation of insurance temperature of close die 120 minutes, naturally cool to room temperature then, promptly obtain self-lubricating high strength cast nylon parts.
The performance perameter of the self-lubricating high strength cast nylon parts of this law preparation is as follows:
| Material property | Unit | Self-lubricating high strength cast nylon |
| Density | g/cm 3 | 1.15-1.21 |
| Tensile strength | MPa | 90-105 |
| Elongation at break | ％ | 25-30 |
| Flexural strength | MPa | 100-110 |
| Ultimate compression strength | MPa | 110-130 |
| Shock strength (breach) | KJ/m 2 | ＞6.8 |
| Shao Shi D hardness | 83-90 | |
| Frictional coefficient | μ | 0.10-0.12 |
Claims (3)
1. the preparation method of self-lubricating high strength cast nylon is characterized in that including following steps:
1) gets the caprolactam monomer of 1000 parts of mass fractions, the nano-TiO that the surface modification of mass fraction 1-20 part is crossed
2The Nano graphite powder of crossing with the basic treatment of mass fraction 1-50 part, join in the reactor, stirring also heats to 120 ℃-140 ℃, vacuumize simultaneously, make the reactor internal gas pressure be lower than 500Pa, continue to stir the hexanolactam melted blend 20-60 minute, obtain containing the hexanolactam melt of nano composite material;
2) sodium hydrate solid of massfraction 2-8 part is joined in the hexanolactam melt that contains nano composite material that step 1) obtains, keep the reactor internal gas pressure to be lower than 500Pa, be warmed up to 140-150 ℃, continue to stir 20-60 minute, obtain the alkaline caprolactam melted blend;
3) logical nitrogen recovers reactor pressure to normal atmosphere in reactor, under the violent stirring condition with the 3-isocyanic ester methylene-3 of massfraction 2-8 part, 5,5-3-methyl cyclohexanol based isocyanate or tolylene diisocyanate join step 2) in the alkaline caprolactam melted blend of gained, stir, be warming up to 140-155 ℃ simultaneously, obtain hexanolactam nylon performed polymer;
4) casting mold is preheating to 165-190 ℃ and constant temperature in heating container, gravity flow of hexanolactam nylon performed polymer or pressurization that step 3) obtains are injected in the mold cavity, the follow-up continuation of insurance temperature of close die 10-120 minute, naturally cool to room temperature then, promptly obtain the self-lubricating high strength cast nylon parts of forming.
2. by the preparation method of the described self-lubricating high strength cast of claim 1 nylon, it is characterized in that described nano-TiO
2Surface modifying treatment be: with nano-TiO
2Join in the dehydrated alcohol, stir fast, obtain TiO
2The dehydrated alcohol mixture; Getting KH-550 or KH-50 coupling agent is dissolved in the less water and and TiO
2The dehydrated alcohol mixture mix, stirred 4-6 hour at 40-60 ℃, the system centrifugation obtains lower floor's paste, puts into baking oven 80-100 ℃ dry for standby.
3. press the preparation method of claim 1 or 2 described self-lubricating high strength cast nylon, the basic treatment method that it is characterized in that described Nano graphite powder is: with the technical grade Nano graphite powder in the sodium hydroxide solution of mass percent concentration 10-30%, 20-70 ℃ is soaked after 12-24 hour down, filter, the Nano graphite powder that obtains is 100-150 ℃ of dry for standby in baking oven.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102492134A (en) * | 2011-12-12 | 2012-06-13 | 中国科学院宁波材料技术与工程研究所 | Nylon/graphite thermal conductive plastic and preparation method and usage thereof |
| CN104004346A (en) * | 2014-05-22 | 2014-08-27 | 广州市南方尼龙制品有限公司 | Super-tough anti-abrasion MC (Monomer Casting) nylon composite material and preparation method thereof |
| CN104761720A (en) * | 2014-01-06 | 2015-07-08 | 王克忠 | Nylon auxiliary agent oil and preparation method and use thereof |
| CN105801840A (en) * | 2016-04-08 | 2016-07-27 | 河南科技大学 | Nanoparticle reinforced self-lubricated cast nylon composite shaft sleeve and manufacturing method thereof |
| CN109441952A (en) * | 2018-12-25 | 2019-03-08 | 浙江双金机械集团股份有限公司 | The processing method of crusher axle sleeve |
| CN110510490A (en) * | 2019-09-24 | 2019-11-29 | 扬州大学 | A kind of special combined idler wheel of elevator, idler wheel processing unit (plant) and idler wheel processing method that can be used in large temperature range |
| CN113370433A (en) * | 2020-03-09 | 2021-09-10 | 邢台中车环保科技有限公司 | Method for producing cast nylon bar |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101509519A (en) * | 2009-04-01 | 2009-08-19 | 贾明君 | Nylon polymerization member water lubricating bearing for ship |
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2011
- 2011-01-18 CN CN 201110009588 patent/CN102153743B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101509519A (en) * | 2009-04-01 | 2009-08-19 | 贾明君 | Nylon polymerization member water lubricating bearing for ship |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102492134A (en) * | 2011-12-12 | 2012-06-13 | 中国科学院宁波材料技术与工程研究所 | Nylon/graphite thermal conductive plastic and preparation method and usage thereof |
| CN102492134B (en) * | 2011-12-12 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Nylon/graphite thermal conductive plastic and preparation method and usage thereof |
| CN104761720A (en) * | 2014-01-06 | 2015-07-08 | 王克忠 | Nylon auxiliary agent oil and preparation method and use thereof |
| CN104761720B (en) * | 2014-01-06 | 2017-04-19 | 王克忠 | Nylon auxiliary agent oil and preparation method and use thereof |
| CN104004346A (en) * | 2014-05-22 | 2014-08-27 | 广州市南方尼龙制品有限公司 | Super-tough anti-abrasion MC (Monomer Casting) nylon composite material and preparation method thereof |
| CN105801840A (en) * | 2016-04-08 | 2016-07-27 | 河南科技大学 | Nanoparticle reinforced self-lubricated cast nylon composite shaft sleeve and manufacturing method thereof |
| CN105801840B (en) * | 2016-04-08 | 2018-03-27 | 河南科技大学 | A kind of nano-particle reinforcement moulded nylon with self-tubricating composite shaft sleeve and its manufacture method |
| CN109441952A (en) * | 2018-12-25 | 2019-03-08 | 浙江双金机械集团股份有限公司 | The processing method of crusher axle sleeve |
| CN110510490A (en) * | 2019-09-24 | 2019-11-29 | 扬州大学 | A kind of special combined idler wheel of elevator, idler wheel processing unit (plant) and idler wheel processing method that can be used in large temperature range |
| CN113370433A (en) * | 2020-03-09 | 2021-09-10 | 邢台中车环保科技有限公司 | Method for producing cast nylon bar |
| CN113370433B (en) * | 2020-03-09 | 2023-04-18 | 邢台中车环保科技有限公司 | Method for producing cast nylon bar |
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