CN106009252A - High-toughness high cold-resistant transparent polypropylene material and preparation method thereof - Google Patents
High-toughness high cold-resistant transparent polypropylene material and preparation method thereof Download PDFInfo
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- CN106009252A CN106009252A CN201610338340.4A CN201610338340A CN106009252A CN 106009252 A CN106009252 A CN 106009252A CN 201610338340 A CN201610338340 A CN 201610338340A CN 106009252 A CN106009252 A CN 106009252A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a high-toughness high cold-resistant transparent polypropylene material which is prepared from a co-polypropylene, a homo-polypropylene, hydrogenated polystyrene-butadiene-styrene triblock copolymer, a crosslinking ethylene-alpha olefine copolymer, a silane crosslinking agent, a nucleating agent, an antioxidant and a processing aid. The weight sum of the co-polypropylene, the homo-polypropylene, a cold-proof flexibilizer agent and the crosslinking ethylene-alpha olefine copolymer is 100 parts. The high-toughness high cold-resistant transparent polypropylene material has good rigidity, low-temperature toughness and heat resistance, good transmission of light of plastics is maintained, the transmittance of a manufactured workpiece is 40% or above, the hollow workpiece manufactured by injection molding and blow molding is formed well, and the high-toughness high cold-resistant transparent polypropylene material is low in damage rate and long in use duration and can be used for producing a transparent hollow kettle.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of high-ductility, high cold-resistant clear acrylic and
Its preparation method.
Background technology
Polypropylene is as kind fastest-rising in general-purpose thermoplastic plastic, the status in economic construction and people's lives
Become more and more important, have a wide range of applications at auto industry, household electrical appliance, electronics, packaging and the aspect such as building materials, furniture.Polypropylene
Being divided into COPP and HOPP, the material property of these two kinds of different polymerization methodses has larger difference, and wherein homopolymerization gathers
The advantages such as it is high that propylene has the transparency, and rigidity is strong, but it has poor toughness, poor dimensional stability, the easy embrittlement of low temperature and easily simultaneously
The shortcoming such as aging, limits its scope of application;And COPP, have that heat resistance is good, good stability of the dimension, processing characteristics
Good and that low-temperature flexibility is good advantage, but there is the shortcomings such as low, the low rigidity of low transparency in many COPPs.
At present for much thermostability, tolerance to cold being required higher goods, simple raw material polypropylene can not be good
Reach requirement, need the superperformance of COPP and HOPP to be combined through modification, thus play poly-
The advantage that propylene is bigger.
Summary of the invention
It is an object of the invention to provide a kind of high-ductility, high cold-resistant clear acrylic and preparation method thereof, pass through
The PP composite material material that the present invention prepares, has good low-temperature flexibility and thermostability, transparency up to 43% with
On, can be used for producing clear hollow kettle body, such as carwash cooling liquid pot.
For achieving the above object, the technical solution used in the present invention is: a kind of high-ductility, high cold-resistant transparent polypropylene material
Material, is prepared from by weight by following component:
COPP 30~55 parts;
HOPP 30~65 parts;
Hydrogenated polystyrene-butadiene-styrene triblock copolymer (SEBS) 2~11 parts;
Cross-linked ethylene-alpha olefin copolymer 5 ~ 15 parts,
Nucleator 0.15~0.35 part;
Silane crosslinker 1.6~2.9 parts;
Antioxidant 0.4~0.65 part;
Processing aid 0.4~1.5 parts;
Described COPP, HOPP, cold-resistant toughened dose, the weight summation of cross-linked ethylene-alpha olefin copolymer be
100 parts.
Scheme further, described COPP is transparent, atactic copolymerized polypropene, under the conditions of 230 DEG C/2.16kg
Melt index be 0.1-4g/10min;Described HOPP melt index 0.1-under the conditions of 230 DEG C/2.16kg
5g/10min。
Further scheme, described cross-linked ethylene-alpha olefin copolymer be by 100 parts of ethylene-alpha-olefin copolymers, 0.6 ~
2.8 parts of cross-linked evocating agents, 0.3 ~ 0.45 part of antioxidant and 0.3 ~ 0.45 part of lubricant carry out mixing, melted crosslinked extrused, tie rod,
Pelletizing prepares.
Scheme further, described ethylene-alpha-olefin copolymer is ethylene-α butylene copolymer or ethylene-α octene copolymer
Thing;Described cross-linked evocating agent is in cumyl peroxide, peroxidized t-butyl perbenzoate, dibenzoyl peroxide
Kind.
Further scheme, described nucleator be two (3,4-dimethylbenzylidene) sorbitol, 2,2-di-2-ethylhexylphosphine oxide (4,
6-di-tert-butyl-phenyl) sodium phosphate, any one in 6-how diformamide based compound.
Scheme further, described silane crosslinker is by vinyltrimethoxy silane, cumyl peroxide and February
Cinnamic acid di-n-butyl tin is 1.5~2.6:0.05~0.3:0.05~0.2 composition in mass ratio.
Scheme further, described antioxidant is by four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane
Ester, tricresyl phosphite (2,4--di-tert-butyl-phenyl) ester octadecyl double with thio-2 acid compounds structure for 1:2:1 in mass ratio
Become.
Scheme further, described processing aid is compounded structure for 1:1 in mass ratio by white mineral oil and ethylene bis stearamide
Become.
Another goal of the invention of the present invention is to provide above-mentioned high-ductility, the method for high cold-resistant clear acrylic, bag
Include following steps:
(1) by COPP, HOPP, cross-linked ethylene-alpha olefin copolymer, silane crosslinker, hydrogenated polystyrene-
Butadiene-styrene triblock copolymer, antioxidant, processing aid, nucleator are poured in temperature control high-speed mixer mixed by proportioning
Close 5-10min, obtain the premix material of precrosslink;The temperature of described mixer is 75-90 DEG C, rotating speed is 500-800r/min;
(2) will (1) first preheat 2~4 minutes in premix material feeding double screw extruder, more evacuated, extrusion, water-cooled,
Pelletizing and being dried, i.e. prepares high heat-resisting, cold-resistant clear acrylic;Wherein the rotating speed of double screw extruder is 300~500
Rev/min, temperature is 170~210 DEG C.
The present invention compared with prior art has the advantage that
(1) COPP and HOPP are combined by the present invention effectively, make the material of preparation toughness, rigidity and
Thermostability aspect reaches balance;
(2) under silane crosslinker effect, silane crosslinker decomposes generation free radical, causes between polypropylene and SEBS macromole
There is chemical crosslink reaction, between macromolecular chain, form chemical bond, and form netted three-dimensional-structure;It addition, cross-linked ethylene-α
Olefin copolymer has more preferable toughening effect than uncrosslinked ethylene-alpha-olefin copolymer.
(3) interpolation of nucleator, makes the nucleus of high polymer increase, and crystallization rate is accelerated, and the crystal granular of crystallization is transparent
Property increase, under comprehensive function, the rigidity of final products, low-temperature flexibility, thermostability, the transparency can be greatly improved.
(4) polypropylene material that the present invention prepares, because being wherein added with nucleator, thus shortens the molding week of comparable product
Phase, improve production efficiency;
(5) polypropylene material that the present invention prepares, the hollow product molding prepared in injection, blowing is good, and breakage rate is low, uses
Timeliness is long;And there is good low-temperature flexibility and thermostability, transparency, up to more than 43%, can be used for producing clear hollow kettle body,
Such as carwash cooling liquid pot.
(6) preparation method of the present invention is reasonable, technique simple, safety and environmental protection.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, following example be only that the present invention will be described rather than
It is limited.
In an embodiment, the method for testing of each physical property is as follows:
Melt flow rate (MFR) is tested according to GB/T 3682-2000;
Hot strength, elongation at break measure according to GB/T 1040.2-2006;
Bending strength, bending modulus measure according to GB/T 9341-2008;
Izod notched impact strength measures according to GB/T 1843-2008;
Load deformation temperature measures according to GB/T 1634.2-2004;
Temperature card softening temperature measures according to GB/T 1633-2000;
Silane crosslinker used in embodiment is by vinyltrimethoxy silane, cumyl peroxide and tin dilaurate two
Normal-butyl stannum is 1.5~2.6:0.05~0.3:0.05~0.2 composition in mass ratio.
Described antioxidant is by four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (1010), Asia
Tricresyl phosphate (2,4-di-tert-butyl-phenyl) ester (168) and the double octadecyl (DSTDP) of thio-2 acid are 1:2:1 in mass ratio
Compounding composition.
Described processing aid is made up of for 1:1 is compounding with ethylene bis stearamide (EBS) in mass ratio white mineral oil.
Cross-linked ethylene-alpha olefin copolymer is to be prepared from by following method: by 7467,0.6 part of DCP of 100 parts of POE,
0.15 part of anti-1010,0.15 part of anti-168,0.2 part of E525,0.1 part of calcium stearate are put into and are carried out in high-speed mixer mixing 2 points
Clock, adds the mixture mixed in double screw extruder and carries out melted crosslinked extrused, tie rod, pelletizing, final must cross-link second
Alkene-alpha olefin copolymer.
COPP 30~55 parts;
SEBS 2-11
Homopolymerisation polyethylene 40~65 parts;
Cross-linked ethylene-alpha olefin copolymer 5 ~ 15 parts,
Embodiment 1
It is 2 parts, cross-linked ethylene-alpha olefin copolymer 5 by COPP 30 parts, 63 parts, cold-resistant toughened dose SEBS of HOPP
Part, nucleant agent N A-11 is 0.25 part, 0.5 part of antioxidant, and processing aid 0.6 part puts into mixing 6min in temperature control high-speed mixer,
Blender temperature controls at 80 DEG C, and rotating speed 600r/min obtains premix material;
Again premix material is fed in double screw extruder, after preheating 3 minutes through evacuation extrusion, water-cooled, pelletizing, be dried, mixed
Even, can be prepared by the regrown material for preparing bumper, wherein 170 DEG C of the pre-tabetisol of extruder, the first melting zone 180
DEG C, the first 190 DEG C of shear at high temperature district, the second 210 DEG C of shear at high temperature district, second melts warm area 205 DEG C, and discharging opening melts warm area
195 DEG C, screw speed is 300 revs/min.
Embodiment 2
By COPP 43 parts, HOPP 40 parts, 15 parts, cold-resistant toughened dose SEBS of cross-linked ethylene-alpha olefin copolymer it is
2 parts, nucleator 3988 is 0.15 part, 0.56 part of antioxidant, and processing aid 1.2 parts is put in temperature control high-speed mixer and mixed
8min, blender temperature controls at 75 DEG C, and rotating speed 800r/min obtains premix material;
Again premix material is fed in double screw extruder, after preheating 3 minutes through evacuation extrusion, water-cooled, pelletizing, be dried, mixed
Even, can be prepared by the regrown material for preparing bumper, wherein 175 DEG C of the pre-tabetisol of extruder, the first melting zone 185
DEG C, the first 190 DEG C of shear at high temperature district, the second 205 DEG C of shear at high temperature district, second melts warm area 200 DEG C, and discharging opening melts warm area
195 DEG C, screw speed is 450 revs/min.
Embodiment 3
It is 2 by COPP 43 parts, HOPP 50 parts, 5 parts, cold-resistant toughened dose SEBS of cross-linked ethylene-alpha olefin copolymer
Part, nucleator TMB-4 is 0.35 part, 0.4 part of antioxidant, and processing aid 0.8 part puts into mixing 5min in temperature control high-speed mixer,
Blender temperature controls at 80 DEG C, and rotating speed 500r/min obtains premix material;
Again premix material is fed in double screw extruder, after preheating 3 minutes through evacuation extrusion, water-cooled, pelletizing, be dried, mixed
Even, can be prepared by the regrown material for preparing bumper, wherein 175 DEG C of the pre-tabetisol of extruder, the first melting zone 185
DEG C, the first 195 DEG C of shear at high temperature district, the second 210 DEG C of shear at high temperature district, second melts warm area 205 DEG C, and discharging opening melts warm area
195 DEG C, screw speed is 500 revs/min.
Embodiment 4
By COPP 58 parts, HOPP 30 parts, 10 parts, cold-resistant toughened dose SEBS of cross-linked ethylene-alpha olefin copolymer it is
2 parts, nucleator 3988 is 0.2 part, 0.48 part of antioxidant, and processing aid 1 part puts into mixing 9min in temperature control high-speed mixer, stirs
The machine temperature of mixing controls at 90 DEG C, and rotating speed 650r/min obtains premix material;
Again premix material is fed in double screw extruder, after preheating 3 minutes through evacuation extrusion, water-cooled, pelletizing, be dried, mixed
Even, can be prepared by the regrown material for preparing bumper, wherein 175 DEG C of the pre-tabetisol of extruder, the first melting zone 185
DEG C, the first 195 DEG C of shear at high temperature district, the second 210 DEG C of shear at high temperature district, second melts warm area 205 DEG C, and discharging opening melts warm area
195 DEG C, screw speed is 350 revs/min.
The product obtained above-described embodiment 1-4 respectively carries out physical property detection by aforesaid standards, its performance such as table 1 below institute
Show:
Table 1:
Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
Melt finger/g/10min | 0.96 | 0.83 | 1.5 | 2.3 |
Hot strength/MPa | 29.7 | 29.1 | 28.1 | 28.3 |
Elongation at break/% | 465 | 547 | 280 | 355 |
Bending strength/MPa | 35.8 | 33.0 | 31.3 | 30.8 |
Bending modulus/MPa | 1536 | 1826 | 1630 | 1811 |
Izod notched impact strength/kJ/m2(23 DEG C) | 40 | 53 | 56 | 49 |
Izod notched impact strength/kJ/m2(-30 DEG C) | 6.3 | 7.3 | 6.9 | 7.6 |
Load deformation temperature/DEG C | 116 | 106 | 108 | 109 |
Temperature card softening temperature/DEG C | 153 | 148 | 145 | 149 |
Light transmittance/% | 43 | 58 | 55 | 49 |
By table 1 embodiment result it can be seen that by cross-linking the made PP composite material material obtained, have good low
Temperature toughness and thermostability, transparency, up to more than 43%, can be used for producing clear hollow kettle body, such as carwash cooling liquid pot etc..In addition
The present invention, compared with pure use HOPP or pure COPP, improves HOPP poor toughness, pure copolymerization poly-third
Alkene thermostability is not enough, the shortcoming of poor transparency.
These embodiments are merely to illustrate the present invention and should not limit the scope of this invention.Additionally, reading this
After bright described content, the present invention is made change or the amendment of the various equivalent form of value, these equivalent form of values by those skilled in the art
Also belong to following claims limited range.
Claims (9)
1. a high-ductility, high cold-resistant clear acrylic, it is characterised in that: it is prepared from by weight by following component:
COPP 30~55 parts;
HOPP 30~65 parts;
Hydrogenated polystyrene-butadiene-styrene triblock copolymer 2~11 parts;
Cross-linked ethylene-alpha olefin copolymer 5 ~ 15 parts,
Nucleator 0.15~0.35 part;
Silane crosslinker 1.6~2.9 parts;
Antioxidant 0.4~0.65 part;
Processing aid 0.4~1.5 parts;
Described COPP, HOPP, cold-resistant toughened dose, the weight summation of cross-linked ethylene-alpha olefin copolymer be
100 parts.
High-ductility the most according to claim 1, high cold-resistant clear acrylic, it is characterised in that: described copolymerization gathers
Propylene is transparent, atactic copolymerized polypropene, and the melt index under the conditions of 230 DEG C/2.16kg is 0.1-4g/10min;Described
HOPP melt index 0.1-5g/10min under the conditions of 230 DEG C/2.16kg.
High-ductility the most according to claim 1, high cold-resistant clear acrylic, it is characterised in that: described crosslinking second
Alkene-alpha olefin copolymer is by 100 parts of ethylene-alpha-olefin copolymers, 0.6 ~ 2.8 part of cross-linked evocating agent, 0.3 ~ 0.45 part of antioxidant
Carry out with 0.3 ~ 0.45 part of lubricant mixing, melted crosslinked extrused, tie rod, pelletizing prepare.
High-ductility the most according to claim 2, high cold-resistant clear acrylic, it is characterised in that: described ethylene-α
Olefin copolymer is ethylene-α butylene copolymer or ethylene-α octene copolymer;Described cross-linked evocating agent is peroxidating diisopropyl
One in benzene, peroxidized t-butyl perbenzoate, dibenzoyl peroxide.
High-ductility the most according to claim 1, high cold-resistant clear acrylic, it is characterised in that: described nucleator
Be two (3,4-dimethylbenzylidene) sorbitol, 2,2-di-2-ethylhexylphosphine oxide (4,6-di-tert-butyl-phenyl) sodium phosphate, 6-how diformazan
Any one in amido compounds.
High-ductility the most according to claim 1, high cold-resistant clear acrylic, it is characterised in that: described crosslinkable silane
Connection agent by vinyltrimethoxy silane, cumyl peroxide and di-n-butyltin dilaurate be in mass ratio 1.5~
2.6:0.05~0.3:0.05~0.2 composition.
High-ductility the most according to claim 1, high cold-resistant clear acrylic, it is characterised in that: described antioxidant is
By four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, tricresyl phosphite (2,4--di-tert-butyl-phenyl) ester
Octadecyl double with thio-2 acid are constituted for 1:2:1 is compounding in mass ratio.
High-ductility the most according to claim 1, high cold-resistant clear acrylic, it is characterised in that: described processing helps
Agent is made up of for 1:1 is compounding with ethylene bis stearamide in mass ratio white mineral oil.
9. prepare the high-ductility as described in any one of claim 1-7, a method for high cold-resistant clear acrylic, its
It is characterised by: comprise the following steps:
(1) by COPP, HOPP, cross-linked ethylene-alpha olefin copolymer, silane crosslinker, hydrogenated polystyrene-
Butadiene-styrene triblock copolymer, antioxidant, processing aid, nucleator are poured in temperature control high-speed mixer mixed by proportioning
Close 5-10min, obtain the premix material of precrosslink;The temperature of described mixer is 75-90 DEG C, rotating speed is 500-800r/min;
(2) will (1) first preheat 2~4 minutes in premix material feeding double screw extruder, more evacuated, extrusion, water-cooled,
Pelletizing and being dried, i.e. prepares high heat-resisting, cold-resistant clear acrylic;Wherein the rotating speed of double screw extruder is 300~500
Rev/min, temperature is 170~210 DEG C.
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CN107936379A (en) * | 2017-12-19 | 2018-04-20 | 芜湖盈奇塑业有限公司 | A kind of preparation method of water horse high-rigidity high-ductility polypropylene plastics |
CN108456366A (en) * | 2018-03-22 | 2018-08-28 | 陕西省石油化工研究设计院 | A kind of high-transparent impact-resistant polypropylene material and preparation method thereof |
CN110628130A (en) * | 2019-09-25 | 2019-12-31 | 东华能源(宁波)新材料有限公司 | Low-shrinkage polypropylene material suitable for 3D printing and preparation method thereof |
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CN107936379A (en) * | 2017-12-19 | 2018-04-20 | 芜湖盈奇塑业有限公司 | A kind of preparation method of water horse high-rigidity high-ductility polypropylene plastics |
CN108456366A (en) * | 2018-03-22 | 2018-08-28 | 陕西省石油化工研究设计院 | A kind of high-transparent impact-resistant polypropylene material and preparation method thereof |
CN110628130A (en) * | 2019-09-25 | 2019-12-31 | 东华能源(宁波)新材料有限公司 | Low-shrinkage polypropylene material suitable for 3D printing and preparation method thereof |
CN110628130B (en) * | 2019-09-25 | 2022-07-08 | 东华能源(宁波)新材料有限公司 | Low-shrinkage polypropylene material suitable for 3D printing and preparation method thereof |
CN110746701A (en) * | 2019-10-10 | 2020-02-04 | 浙江亚兰特新材料科技有限公司 | Polypropylene composition and preparation method thereof |
CN113402753A (en) * | 2020-07-31 | 2021-09-17 | 江苏品升管业股份有限公司 | Processing method of cold-resistant pipeline |
CN113912941A (en) * | 2021-10-26 | 2022-01-11 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
CN114276624A (en) * | 2021-12-15 | 2022-04-05 | 广东特帅科技股份有限公司 | High-molecular modified material of high-cold-resistance UV-resistant smart logistics pallet |
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