CN109517369A - Rapid shaping nylon masterbatch and the preparation method and application thereof - Google Patents
Rapid shaping nylon masterbatch and the preparation method and application thereof Download PDFInfo
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- CN109517369A CN109517369A CN201710855640.4A CN201710855640A CN109517369A CN 109517369 A CN109517369 A CN 109517369A CN 201710855640 A CN201710855640 A CN 201710855640A CN 109517369 A CN109517369 A CN 109517369A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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Abstract
The present invention relates to a kind of rapid shaping nylon masterbatch and the preparation method and application thereof.The nylon masterbatch contains the component of following parts by weight: 1~98 part of nylon 8,0~8 part of toughener, 0.1~2.5 part of antioxidant, 2.0~7.5 parts of lubricant, 0.1~2.0 part of nucleating agent.The preparation method of the masterbatch is that each component carries out ingredient in proportion, is then uniformly mixed by double screw extruder, after sufficiently drying under dry at 80 DEG C.The master batch weight percentage 4~20% is added in the mixture of nylon 6, nylon66 fiber or two kinds of polymer, mobility, release property and the molding cycle of nylon can be obviously improved.Product is widely used in nylon syringe molding, the production of the nylon products big especially suitable for thin-walled and draw ratio.
Description
Technical field
The present invention relates to polymer material and processing technique fields, specifically, the present invention relates to a kind of fast shaping nylons
Imperial masterbatch and the preparation method and application thereof.
Background technique
In five large-engineering plastics field, nylon is a kind of product that application range is most wide, application field is most.Nylon is one
Class high mechanical strength, fatigue durability are prominent, softening temperature is high, surface is smooth, coefficient of friction is small, wear-resisting property is good, corrosion-resistant, energy
The excellent a kind of high molecular material of self-extinguishment, electric property is the ideal material to mould Dai Gang, is often used to process various wear-resisting
High-intensitive part.Nylon products have been deep into human being's production and every field of living to obtain, and are such as widely used in communications and transportation, boat
Empty space flight, electronic apparatus, architectural engineering, mechanical equipment, mining etc..
In nylon family, most widely used is nylon 6 and nylon66 fiber, and the high comprehensive performance of two kinds of polymer is being made
Making wear part, drive mechanism part, household appliance components, automobile manufacture part, screw rod prevents machine components, chemical machinery zero
Quite favored in the industry such as part, chemical industry equipment, such as turbine, gear, bearing, impeller, crank, instrument board, drive shaft, valve, leaf
Piece, screw rod, high pressure washer, screw, nut, sealing ring, shuttle, set letter, axle sleeve connector, band etc..
Application of the nylon in engineering plastics field mostly uses injection moulding, this crystallization rate, mobility, demoulding to nylon
More stringent requirements are proposed for the performances such as property, resistance to thermal degradation and thermal oxidation.But nylon 6 and nylon66 fiber are hypocrystalline polymerizations
Object, in injection moulding, injection cycle is long, and injection pressure is big, it is desirable that injection temperature mold temperature is low, causes in production thin-walled system
The disadvantages of the disadvantages of product internal stress is big when product or big L/D ratio product, poor toughness, so that influencing the comprehensive performance and limit of product
Make its application field.
By taking nylon cable tie as an example, this is a kind of big L/D ratio product, it is desirable that nylon raw material good fluidity, crystallization rate is fast,
Easy mold release.Non-modified nylon raw material is not able to satisfy the production requirement of nylon cable tie, needs to be injected at very high temperatures
Type, the often higher than decomposition starting temperature of nylon, long so as to cause nylon cable tie molding cycle, demoulding is difficult, and toughness of products is poor
The disadvantages of.And rapid shaping nylon masterbatch can be obviously improved the mobility of nylon, improve the crystallization rate of nylon, produce band
Product can realize demoulding at higher temperatures, to realize the shortening injection moulding period, improve band toughness, can satisfy
It is used at lower temperature.
Summary of the invention
Object of the present invention is to improve the mobility of nylon (such as nylon 6 and nylon66 fiber), improve nylon crystallization rate, improvement
Nylon demolding performace shortens in thin-wall product or big L/D ratio product manufacturing field and is injection moulded the period, improves the heat of nylon surely
Dimensional stability that is qualitative, improving nylon products etc., to realize the purpose for improving the synthesis service performance of nylon products.
The method of traditional improvement nylon processing performance is to be modified processing, before being injection moulded, is changed with being blended
Nucleating agent, antioxidant, lubricant and other auxiliary agents or modifying agent are distributed to nylon sheet by the mode of property in a manner of blending and modifying
In body.When the disadvantage of conventional method is by once modified processing, nylon undergoes a hot-working, and heat occurs for portions of nylon
Degradation or hydrolytic degradation, this not only reduces the viscosity of nylon, and the mechanical degradation of nylon products, product yellow but will be caused to refer to
Number increases, and manufacturing cost increases.
In order to achieve the above technical purposes, it the technical scheme is that preparing a kind of rapid shaping nylon masterbatch, is infusing
When penetrating molding masterbatch and nylon raw material can be used after mixing by mixing apparatus, effectively avoids above-mentioned processing problems
Occur.
A kind of rapid shaping nylon masterbatch, the component containing following parts by weight:
1~98 part of nylon 8,0~8 part of toughener, 0.1~2.5 part of antioxidant, 2.0~7.5 parts of lubricant, nucleating agent
0.1~2.0 part.
Preferably, the rapid shaping nylon masterbatch, the component containing following parts by weight:
5~95 parts of nylon 8,0~5.0 part of toughener, 0.5~2.0 part of antioxidant, 3.0~6.0 parts of lubricant, nucleation
0.5~1.5 part of agent.
Further, above-mentioned rapid shaping nylon masterbatch, component total amount are 100 parts.
In a preferable embodiment of the invention, above-mentioned rapid shaping nylon masterbatch is by following weight percentage
Group is grouped as:
Nylon 8 8.0~94%, toughener 0~5.0%, antioxidant 0.75~1.25%, lubricant 3.0~5.0%,
Nucleating agent 0.75~1.25%.
Further, the nylon is or mixtures thereof amorphous nylon resins；The amorphous nylon resins include Buddhist nun
Dragon 610, nylon 612, nylon 1010, nylon 11, nylon 12, nylon 1212, nylon 6, nylon66 fiber etc.；Preferably, the nylon
For the mixture of one or both of nylon 6, nylon66 fiber.
Further, the opposite sulfuric acid viscosity of the nylon 6 is 2.30~3.20；The opposite sulfuric acid viscosity of nylon66 fiber is
2.40~3.20.
Conventional method in that art detection can be used in opposite sulfuric acid viscosity of the present invention.
Further, the toughener includes ethylene-acrylate (salt) copolymer, ethylene-acrylate (salt)-Malaysia
Acid anhydride copolymer, maleic anhydride grafted ethene-acetate ethylene copolymer, maleic anhydride grafted ethene-alpha olefin copolymer, ethylene-
Acrylic acid-acrylic ester (salt), ethylene-maleic acid (ester)-glycidyl acrylate, maleic anhydride grafted polyethylene, horse
One of maleic anhydride grafted polypropylene, maleic anhydride-styrene copolymers, maleic anhydride modified ternary isopropyl rubber etc. are several
The mixture of kind.
Further, the antioxidant includes N, and N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono)
Hexamethylene diamine, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2.4- di-tert-butyl-phenyl] phosphorous acid
Ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, bis- (2,4-DTBP) pentaerythrites
The mixture of one or more of diphosphites, antioxidant ST-181A, cuprous iodide, potassium iodide etc..
Further, the lubricant includes calcium stearate, zinc stearate, odium stearate, octadecanol, double stearic acid
Aluminium, ethylenebis stearamide, N, N '-ethylenebis stearic amide, silicone powder, amido silicon oil, polyethylene wax, polyoxyethylene
The mixture of one or more of alkene wax etc..
Further, the nucleating agent includes that talcum powder, sodium phenyl phosphinate, phenyl zinc hypophosphite, modified organic illiteracy are de-
One of soil, calcirm-fluoride, P22, calcining wollastonite, calcined alumina, CAV102, molybdenum disulfide, graphite, KL-102 etc. or several
The mixture of kind.
The present invention also provides the preparation methods of above-mentioned rapid shaping masterbatch, including take each raw material mixed according to the ratio as needed
It is even, it is dry by double screw extruder extrusion granulation.
Further, by mixed material, melt blending extrusion granulation, extruder temperature are each on parallel dual-screw extruding machine
Area's temperature setting be respectively as follows: from main feeding 100-150 DEG C, 130-180 DEG C, 160-200 DEG C, 200-230 DEG C, 240-260 DEG C,
245-275 DEG C, 220-250 DEG C, 220-250 DEG C, 220-250 DEG C, 220-250 DEG C, die temperature are 210-245 DEG C.
Further, by mixed material on parallel dual-screw extruding machine melt blending extrusion granulation, extruder temperature
Each area's temperature setting be respectively as follows: from main feeding 120 DEG C, 160 DEG C, 180 DEG C, 220 DEG C, 250 DEG C, 260 DEG C, 230 DEG C, 240 DEG C,
240 DEG C, 240 DEG C, die temperature are 235 DEG C.
Further, parallel dual-screw extruding machine can be used.
The drying preferably carries out under the conditions of 80 DEG C.It is general dry to moisture content≤%.
The invention also includes above-mentioned rapid shaping masterbatch to prepare the application on nylon products.
Additive amount of the rapid shaping masterbatch of the present invention in nylon products is 2~25 weight %.Specific dosage according to
Depending on auxiliary agent type and its content contained in nylon resin.
Further, the nylon products include thin wall injection shaped article, including electric power connector, electronic/electrical device are inserted
The thin wall injections shaped article such as head, route panel element, nylon furniture.
Masterbatch of the present invention applies also for the big L/D ratios products such as injection moulding production nylon cable tie.
As described above, nylon of the present invention is or mixtures thereof amorphous nylon resins；The amorphous nylon resins
Including nylon 610, nylon 612, nylon 1010, nylon 11, nylon 12, nylon 1212, nylon 6, nylon66 fiber etc.；Preferably, institute
State the mixture that nylon is one or both of nylon 6, nylon66 fiber.
Rapid shaping masterbatch of the present invention does not influence nylon syringe forming temperature and pressure, lesser in production draw ratio
When thin-walled nylon product, 5~10 DEG C of injection temperature can be reduced and injection pressure remains unchanged or injection temperature remains unchanged, slightly
Edge down low injection pressure.
Rapid shaping masterbatch of the present invention can improve the mobile performance of nylon, be full of melt within the shorter time
Mold.
Rapid shaping masterbatch of the present invention can obviously accelerate nylon crystallization rate, crystallize after reduction steady to nylon size
It qualitatively influences, improves the dimensional stability of injected articles.
Rapid shaping masterbatch of the present invention can reduce the injection moulding time 1~5 second.
Rapid shaping masterbatch of the present invention can improve the low-temperature flexibility of injection nylon product.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
Embodiment 1
Rapid shaping nylon masterbatch, is grouped as by the group of following weight percentage:
Nylon 6, opposite sulfuric acid viscosity 2.45, dosage 93.0%,
β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, potassium iodide compound (three with cuprous iodide
Between ratio be 3:2:1), dosage 1.0%,
Organo montmorillonite, dosage 1.5%,
N, N '-ethylenebis stearic amide, polyethylene wax and amido silicon oil compounding (ratio is 1:1 between the two), are used
Amount 4.5%.
The present embodiment also provides the preparation method of above-mentioned rapid shaping masterbatch, including each raw material is taken to mix according to the ratio, will mix
Material melt blending extrusion granulation on parallel dual-screw extruding machine is closed, each area's temperature setting of extruder temperature is divided from main feeding
Not are as follows: 120 DEG C, 160 DEG C, 180 DEG C, 220 DEG C, 250 DEG C, 260 DEG C, 230 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, die temperature are
235℃.Extrudate is dried in vacuo 6 hours under the conditions of 80 DEG C, then in vacuum packaging of aluminium foil bag.
Embodiment 2
Rapid shaping nylon masterbatch, is grouped as by the group of following weight percentage:
Nylon 6, opposite sulfuric acid viscosity 2.65, dosage 93.0%,
β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and three [2.4- di-tert-butyl-phenyl] phosphorous
Acid esters compounding, dosage 1.0%,
Talcum powder, phenyl zinc hypophosphite and organo montmorillonite compounding (ratio is 1:1:3 between three), dosage 1.5%,
N, N '-ethylenebis stearic amide, calcium stearate and silicone powder compounding (ratio is 4:2:1 between three), are used
Amount 4.5%.
The preparation method is the same as that of Example 1 for the present embodiment rapid shaping masterbatch.
Embodiment 3
Rapid shaping nylon masterbatch, is grouped as by the group of following weight percentage:
Nylon 6, opposite sulfuric acid viscosity 2.80, dosage 93.0%,
N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine compound (the two with cuprous iodide
Between ratio be 1:1), dosage 1.0%,
CAV102 and talcum powder compounding (ratio between the two is 3:1), dosage 1.5%,
N, N '-ethylenebis stearic amide, zinc stearate and polyethylene glycol oxide compounding (between three ratio be 4:2:
2), dosage 4.5%.
The preparation method is the same as that of Example 1 for the present embodiment rapid shaping masterbatch.
Embodiment 4
Rapid shaping nylon masterbatch, is grouped as by the group of following weight percentage:
Nylon 6, opposite sulfuric acid viscosity 2.45, dosage 93.0%,
Bis- (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites and three [2.4- di-tert-butyl-phenyl] phosphite esters
Compounding (ratio between the two is 1:1), dosage 1.0%,
P22 and talcum powder, organo montmorillonite compounding (ratio is 2:1:6 between three), dosage 1.5%,
N, N '-ethylenebis stearic amide, calcium stearate and silicone powder compounding (ratio is 1:1:1 between three), are used
Amount 4.5%.
The preparation method is the same as that of Example 1 for the present embodiment rapid shaping masterbatch.
Embodiment 5
Rapid shaping nylon masterbatch, is grouped as by the group of following weight percentage:
Nylon 6, opposite sulfuric acid viscosity 2.65, dosage 88.0%,
Maleic anhydride grafting ethylene propylene diene rubber, dosage 5.0%,
Bis- (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites and three [2.4- di-tert-butyl-phenyl] phosphite esters
Compounding (ratio between the two is 1:1), dosage 1.0%,
P22 and talcum powder, organo montmorillonite compounding (ratio is 1:1:3 between three), dosage 1.5%,
N, N '-ethylenebis stearic amide, calcium stearate and silicone powder compounding (ratio is 2:2:1 between three), are used
Amount 4.5%.
The preparation method is the same as that of Example 1 for the present embodiment rapid shaping masterbatch.
Experimental example
By taking band manufactures as an example, Example 1-5 rapid shaping nylon masterbatch is mixed with PA66, PA6 respectively pricks with tradition
Product with technique production compares (the model 4.2mmX300mm of assessment band), is as follows:
The experimental results showed that, in band manufacture view, have reduces the cost of raw material, improves cryogenic property the present invention above
With heat resistant performance, while molding cycle is not influenced, does not reduce production efficiency, increase while improving band properties of product
Add profit margin.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of rapid shaping nylon masterbatch, which is characterized in that the component containing following parts by weight:
1~98 part of nylon 8,0~8 part of toughener, 0.1~2.5 part of antioxidant, 2.0~7.5 parts of lubricant, nucleating agent 0.1~
2.0 part.
2. rapid shaping nylon masterbatch according to claim 1, which is characterized in that the component containing following parts by weight:
5~95 parts of nylon 8,0~5.0 part of toughener, 0.5~2.0 part of antioxidant, 3.0~6.0 parts of lubricant, nucleating agent 0.5
~1.5 parts.
3. rapid shaping nylon masterbatch according to claim 1 or 2, which is characterized in that its component total amount is 100 parts.
4. rapid shaping nylon masterbatch according to claim 1, which is characterized in that by the component of following weight percentage
Composition:
Nylon 8 8.0~94.0%, toughener 0~5.0%, antioxidant 0.75~1.25%, lubricant 3.0~5.0%, at
Core agent 0.75~1.25%.
5. rapid shaping nylon masterbatch according to claim 1-4, which is characterized in that the nylon is aliphatic
Or mixtures thereof nylon resin；Preferably, the amorphous nylon resins include nylon 610, nylon 612, nylon 1010, nylon
11, nylon 12, nylon 1212, nylon 6, nylon66 fiber.
6. rapid shaping nylon masterbatch according to claim 5, which is characterized in that the nylon is nylon 6, in nylon66 fiber
One or two kinds of mixtures；
Preferably, the opposite sulfuric acid viscosity of the nylon 6 is 2.30~3.20；The opposite sulfuric acid viscosity of nylon66 fiber be 2.40~
3.20。
7. rapid shaping nylon masterbatch according to claim 1-6, which is characterized in that
The toughener includes ethylene-acrylate (salt) copolymer, ethylene-acrylate (salt)-copolymer-maleic anhydride, horse
Maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted ethene-alpha olefin copolymer, ethylene-acrylic acid-acrylic acid
Ester (salt), ethylene-maleic acid (ester)-glycidyl acrylate, maleic anhydride grafted polyethylene, maleic anhydride grafting poly- third
The mixture of one or more of alkene, maleic anhydride-styrene copolymers, maleic anhydride modified ternary isopropyl rubber；With/
Or,
The antioxidant includes N, and N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2.4- di-tert-butyl-phenyl] phosphite esters, four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] it is pentaerythritol ester, bis- (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites, anti-
The mixture of one or more of oxygen agent ST-181A, cuprous iodide, potassium iodide；And/or
The lubricant includes calcium stearate, zinc stearate, odium stearate, octadecanol, double stearic acid aluminium, ethylenebis 18
Amide, N, one of N '-ethylenebis stearic amide, silicone powder, amido silicon oil, polyethylene wax, polyethylene glycol oxide wax or
Several mixtures；And/or
The nucleating agent include talcum powder, sodium phenyl phosphinate, phenyl zinc hypophosphite, modified organo montmorillonite, calcirm-fluoride, P22,
Calcine the mixture of one or more of wollastonite, calcined alumina, CAV102, molybdenum disulfide, graphite, KL-102.
8. the preparation method of any one of the claim 1-7 rapid shaping masterbatch, which is characterized in that including as needed by matching
It is dry by double screw extruder extrusion granulation than taking each raw material to mix.
9. preparation method according to claim 8, which is characterized in that melt mixed material on parallel dual-screw extruding machine
Melt blending extrusion granulation, each area's temperature setting of extruder temperature be respectively as follows: from main feeding 100-150 DEG C, 130-180 DEG C,
160-200℃、200-230℃、240-260℃、245-275℃、220-250℃、220-250℃、220-250℃、220-250
DEG C, die temperature is 210-245 DEG C；
Preferably, by mixed material on parallel dual-screw extruding machine melt blending extrusion granulation, each area's temperature of extruder temperature
Setting be respectively as follows: from main feeding 120 DEG C, 160 DEG C, 180 DEG C, 220 DEG C, 250 DEG C, 260 DEG C, 230 DEG C, 240 DEG C, 240 DEG C,
240 DEG C, die temperature is 235 DEG C.
10. the fast short-term training of the described in any item rapid shaping masterbatch of claim 1-7 or the preparation of claim 8 or 9 the methods
Type masterbatch is preparing the application on nylon products；
Preferably, additive amount of the rapid shaping masterbatch in nylon products is 2~25 weight %；And/or
Preferably, the nylon products are thin wall injection shaped article, including electric power connector, electronic/electrical device plug, wiring board
Element, furniture.
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| CN110591100A (en) * | 2019-09-25 | 2019-12-20 | 杭州聚丰新材料有限公司 | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof |
| CN110655785A (en) * | 2019-10-14 | 2020-01-07 | 张家港绿洲新材料科技有限公司 | Nylon master batch suitable for low-temperature nylon cable tie and preparation method and application thereof |
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| CN110591100A (en) * | 2019-09-25 | 2019-12-20 | 杭州聚丰新材料有限公司 | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof |
| CN110591100B (en) * | 2019-09-25 | 2020-08-04 | 杭州聚丰新材料有限公司 | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof |
| CN110655785A (en) * | 2019-10-14 | 2020-01-07 | 张家港绿洲新材料科技有限公司 | Nylon master batch suitable for low-temperature nylon cable tie and preparation method and application thereof |
| CN110746769A (en) * | 2019-10-14 | 2020-02-04 | 张家港绿洲新材料科技有限公司 | Nylon master batch suitable for outdoor ultraviolet-resistant low-temperature nylon cable tie and preparation method and application thereof |
| CN110655785B (en) * | 2019-10-14 | 2022-04-19 | 张家港绿洲新材料科技有限公司 | Nylon master batch suitable for low-temperature nylon cable tie and preparation method and application thereof |
| CN110951243A (en) * | 2019-12-05 | 2020-04-03 | 常州润企安塑业有限公司 | Self-lubricating composite nylon material and preparation method thereof |
| CN111019335A (en) * | 2020-01-03 | 2020-04-17 | 无锡巨旺塑化材料有限公司 | Nylon cable tie master batch and preparation method thereof |
| CN112646364A (en) * | 2020-12-18 | 2021-04-13 | 意得凯(深圳)科技有限责任公司 | High-elasticity transparent mirror frame material |
| CN113150327A (en) * | 2021-04-24 | 2021-07-23 | 上海谦宇新材料有限公司 | Nylon functional master batch and preparation method and application thereof |
| CN113214640A (en) * | 2021-05-20 | 2021-08-06 | 昆山运融新材料科技有限公司 | Preparation method of super-toughness composite modified nylon master batch |
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