CN107501719A - One kind polymer-filled master batch and preparation method thereof made of polypropylene reclaimed material - Google Patents
One kind polymer-filled master batch and preparation method thereof made of polypropylene reclaimed material Download PDFInfo
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- CN107501719A CN107501719A CN201610426021.9A CN201610426021A CN107501719A CN 107501719 A CN107501719 A CN 107501719A CN 201610426021 A CN201610426021 A CN 201610426021A CN 107501719 A CN107501719 A CN 107501719A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
Abstract
The invention discloses one kind made of polypropylene reclaimed material polymer-filled master batch and preparation method thereof, it is by polypropylene reclaimed material, low density polyethylene (LDPE), polypropylene grafted maleic anhydride, inorganic mineral filler, 2,5 dimethyl 2,5 pairs of (tert-butyl peroxy base) hexanes, antioxidant, lubricants, blended, extrusion prepare gained.The present invention solves the problems such as cost height of Conventional filler master batch in the market, bad dispersibility, poor compatibility, while extends the use range of regenerated plastics.Filler parent granule after the invention working process can be used for being widely used in the filling-modified of the materials such as automobile, pipeline, cable, and can significantly be modified raw material in the case where meeting properties of product requirement reduces cost, improves the use value of regenerated plastics.
Description
Technical field
The invention belongs to field of compound material, and in particular to one kind polymer-filled master batch made of polypropylene reclaimed material
And preparation method thereof.
Background technology
For correlated performances such as the mechanical performance of reinforced plastic material, density, typically add a little modifying agent and it is entered
Row is modified, originally modifying plastics directly use powder at filling-modified aspect, and this modification mode on the one hand can be to production environment
There is larger pollution, the addition of another aspect powder is poor at scattered aspect, influences final products performance.In recent years, as plastics change
The continuous renewal and development of property technology, using filler parent granule as the filling-modified production form for becoming many enterprises,
Effective improvement is obtained in terms of pollution and processing technology.
At present, the base-material that the substantial amounts of filler parent granule of in the market mainly uses is virgin material polypropylene, low density polyethylene (LDPE), polyene
Olefin elastomer (POE) etc., the cost of raw material aspect of production are higher.And it is filled master batch using regenerated plastics as base-material
Production, then corresponding auxiliary agent is equipped with, the cost of raw material can not only be effectively reduced, and dispersive property, compatibility can be obtained
Good filler parent granule, modifying plastics industry, such as automobile, pipeline, cable can be widely used in.
The content of the invention
It is an object of the invention to provide one kind made of polypropylene reclaimed material polymer-filled master batch and its preparation side
Method.
To achieve the above object, the technical solution adopted by the present invention is：One kind polymer made of polypropylene reclaimed material
Filler parent granule, it is prepared by weight by following components：
Described polypropylene reclaimed material be after recovery through sorting, cleaning, crushing, drying obtained injection grade polypropylene, its
Moisture content is less than 3% less than 0.5%, combustion residue, and melt index is 15-60g/10min under the conditions of 2.16kg/230 DEG C.
The low density polyethylene (LDPE) melt index is 50~60g/10min under the conditions of 2.16kg/230 DEG C.
Grafting rate >=1% of the polypropylene grafted maleic anhydride, weight average molecular weight >=30000.
Described inorganic mineral filler is the one or more in talcum powder, calcium carbonate or mica, the mesh of its particle diameter >=3000.
The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (1010) and 6-
The just pungent sulfenyl -1,3,5- triazines (antioxidant 565) of (4- hydroxyl -3,5- di-t-butyls phenylamino) -2,4- two are 1 in mass ratio:4
Compounded.
Described lubricant is that White Mineral Oil, ethylene bis stearamide (EBS) and calcium stearate are 2 in mass ratio:1:1 is carried out
Compounding.
Another goal of the invention of the present invention is to provide a kind of method for preparing above-mentioned polymer-filled master batch, including following
Step：
(1) by the polypropylene reclaimed material of drying process, low density polyethylene (LDPE), polypropylene grafted maleic anhydride, antioxidant,
Lubricant is poured into temperature control high-speed mixer by formula rate and mixes 2-3min；The temperature of the mixer be 75 DEG C -90 DEG C, turn
Speed is 500-800r/min；
(2) add inorganic mineral filler in the compound in (1), be uniformly added into whipping process 2,5- dimethyl-
After 2,5- double (tert-butyl peroxy base) hexanes, continue to be stirred 10-15min, obtain premix；
(3) L/D=44 is put into premix:In 1 double screw extruder, after first preheating 2~4 minutes, then through molten
Melt, extrude, vacuumizing, be air-cooled, pelletizing and drying, i.e., obtained filler parent granule, wherein double screw extruder temperature setting are：Melt in advance
140~155 DEG C of area, the first 190~200 DEG C of melting zone, the first 200~210 DEG C of shear at high temperature area, the second shear at high temperature area 210
~220 DEG C, the second 200~210 DEG C of warm area of melting, discharging opening 190~200 DEG C of warm area of melting；Process double screw extruder
Rotating speed be 300~500 revs/min.
The present invention has following advantages compared with prior art：
(1) present invention introduces highly polar reactive base by adding polypropylene grafted maleic anhydride in polypropylene reclaimed material
Group, makes material have high polarity and reactivity, greatly improves the compatibility of polypropylene and mineral filler；
(2) on the one hand polypropylene reclaimed material can be significantly increased in double (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5-
The degree of cross linking, increase composition melt index, improve combination physics characteristic；On the other hand it is common with polypropylene grafted maleic anhydride
Effect reaches combines closely with polymer, significantly improves intensity, cohesion, dispersive property of material etc., finally makes to be made
Master batch there is good dispersiveness, compatibility；
(3) purpose that the present invention adds low density polyethylene (LDPE) is the viscosity of melt when adjusting melting extrusion, makes melt dispersion
It is good, it is well mixed, broken strip when solving extrusion, stops up the problems such as die head.
(4) the special antioxidant formed is mixed in the present invention with antioxidant 565 using antioxidant 1010, its dosage is only
0.01-0.02 parts, greatly reduce the dosage of antioxidant, and common antioxidant dosage minimum 0.5% or so；And can protected material
During production, processing and final use thermal oxidative degradation does not occur for material, so as to maintain the mechanical property of material well.
(5) the cost height of the invention for solving Conventional filler master batch in the market, bad dispersibility, poor compatibility etc. are asked
Topic, while extend the use range of regenerated plastics.Filler parent granule after the invention working process can be used for being widely used in vapour
The materials such as car, pipeline, cable it is filling-modified, meet properties of product requirement in the case of can significantly be modified raw material reduction into
This, improves the use value of regenerated plastics.
Embodiment
With reference to embodiment, the invention will be further described, following examples be only that the present invention will be described rather than
It is limited.
It is 1 in mass ratio by antioxidant 1010 and antioxidant 565 that antioxidant, which is,:4 carry out compounding composition.
It is 2 in mass ratio by White Mineral Oil, ethylene bis stearamide (EBS) and calcium stearate that described lubricant, which is,:1:1 enters
Row compounding composition.
Polypropylene reclaimed material is from, through sorting, cleaning, crushing, drying obtained injection grade polypropylene, it contains after recovery
It is 15-60g/10min under the conditions of 2.16kg/230 DEG C that water rate is less than 3%, melt index less than 0.5%, combustion residue.
Embodiment 1
By 10 parts, 10 parts low density polyethylene (LDPE)s of polypropylene reclaimed material, 5 parts of polypropylene grafted maleic anhydride, antioxidant 0.01
Part, 1.6 parts of lubricant be put into temperature control high-speed mixer and mix 2min, temperature control is at 80 DEG C, rotating speed 700r/min；Then will
In 85 parts of addition high-speed mixers of inorganic mineral filler calcium carbonate, stir while being uniformly added into 2,5- dimethyl -2,5- pair
1.7 parts of (tert-butyl peroxy base) hexane, high mixer rotating speed are controlled in 750r/min, are continued to stir 12min after adding, are premixed
Material；Premix is finally fed into L/D=44:In 1 double screw extruder, preheating is after 3 minutes, then through melt, extrude, take out it is true
Empty, air-cooled, pelletizing and drying, that is, be made filler parent granule, and each area's temperature of wherein double screw extruder is：Pre- 140 DEG C of tabetisol, the
One 195 DEG C of melting zone, the first 205 DEG C of shear at high temperature area, the second 210 DEG C of shear at high temperature area, the second 205 DEG C of warm area of melting, discharging
Mouth 195 DEG C of warm area of melting, screw speed are 350 revs/min.
It is 25 in mass ratio by filler parent granule obtained above and polypropylene：75 mixed after again through melting, extruding
Composite.
Embodiment 2
By 13 parts, 20 parts low density polyethylene (LDPE)s of polypropylene reclaimed material, 2 parts of polypropylene grafted maleic anhydride, antioxidant 0.02
Part, 3 parts of lubricant be put into temperature control high-speed mixer and mix 3min, temperature control is at 75 DEG C, rotating speed 600r/min；Then by nothing
In 30 parts of 55 parts of machine mineral filler calcium carbonate, talcum powder addition high-speed mixers, 2,5- dimethyl -2,5- are double (tert-butyl peroxy base)
1.6 parts of hexane, high mixer rotating speed are controlled in 650r/min, are continued to stir 15min after adding, are obtained premix；Finally will premix
In material feeding double screw extruder, preheating is after 2 minutes, then through melting, extruding, vacuumizing, air-cooled, pelletizing and drying, that is, make
Filler parent granule is obtained, each area's temperature of wherein double screw extruder is：Pre- 155 DEG C of tabetisol, the first 200 DEG C of melting zone, the first high temperature
210 DEG C of shear zone, the second 220 DEG C of shear at high temperature area, the second 210 DEG C of warm area of melting, discharging opening 200 DEG C of warm area of melting, screw rod turn
Speed is 400 revs/min.
It is 25 in mass ratio by filler parent granule obtained above and polypropylene：75 mixed after again through melting, extruding
Composite.
Embodiment 3
By 15 parts, 30 parts low density polyethylene (LDPE)s of polypropylene reclaimed material, 5 parts of polypropylene grafted maleic anhydride, antioxidant 0.01
Part, 2.5 parts of lubricant be put into temperature control high-speed mixer and mix 3min, temperature control is at 90 DEG C, rotating speed 800r/min；Then will
In 45 parts of 35 parts of inorganic mineral filler mica powder, talcum powder addition high-speed mixers, stir while being uniformly added into 2,5- bis-
Double 1.5 parts of (tert-butyl peroxy base) hexanes of methyl -2,5-, high mixer rotating speed control in 800r/min, continue to stir after adding
12min, obtain premix；Finally premix is fed in double screw extruder, preheating is after 3 minutes, then through melting, extruding,
Vacuumize, be air-cooled, pelletizing and drying, i.e., obtained filler parent granule, each area's temperature of wherein double screw extruder are：Pre- tabetisol 140
DEG C, the first 190 DEG C of melting zone, the first 200 DEG C of shear at high temperature area, the second 210 DEG C of shear at high temperature area, the second 200 DEG C of warm area of melting,
Discharging opening melts 190 DEG C of warm area, and screw speed is 300 revs/min.
It is 25 in mass ratio by filler parent granule obtained above and polypropylene：75 mixed after again through melting, extruding
Composite.
Embodiment 4
By 20 parts, 10 parts low density polyethylene (LDPE)s of polypropylene reclaimed material, 5 parts of polypropylene grafted maleic anhydride, antioxidant 0.02
Part, 1.5 parts of lubricant be put into temperature control high-speed mixer and mix 3min, temperature control is at 75 DEG C, rotating speed 600r/min；Then will
In 75 parts of addition high-speed mixers of inorganic mineral filler talcum powder, stir while being uniformly added into 2,5- dimethyl -2,5- pair
1.5 parts of (tert-butyl peroxy base) hexane, high mixer rotating speed are controlled in 500r/min, are continued to stir 10min after adding, are premixed
Material；Finally premix is fed in double screw extruder, preheating is after 2 minutes, then through melting, extruding, vacuumizing, it is air-cooled, cut
Grain and dry, i.e., obtained filler parent granule, each area's temperature of wherein double screw extruder are：Pre- 145 DEG C of tabetisol, the first melting zone
200 DEG C, the first 205 DEG C of shear at high temperature area, the second 215 DEG C of shear at high temperature area, the second 205 DEG C of warm area of melting, discharging opening melting temperature
195 DEG C of area, screw speed are 500 revs/min.
It is 25 in mass ratio by filler parent granule obtained above and polypropylene：75 mixed after again through melting, extruding
Composite.
Embodiment 5
By 16 parts, 10 parts low density polyethylene (LDPE)s of polypropylene reclaimed material, 4 parts of polypropylene grafted maleic anhydride, antioxidant 0.02
Part, 2 parts of lubricant be put into temperature control high-speed mixer and mix 2min, temperature control is at 90 DEG C, rotating speed 500r/min；Then by nothing
In 30 parts of 50 parts of machine mineral filler calcium carbonate, mica powder addition high-speed mixers, stir while being uniformly added into 2,5- diformazans
Double 1.6 parts of (tert-butyl peroxy base) hexanes of base -2,5-, high mixer rotating speed are controlled in 600r/min, continue to stir 13min after adding,
Obtain premix；Finally premix is fed in double screw extruder, preheating is after 2 minutes, then through melting, extruding, vacuumizing,
Air-cooled, pelletizing and drying, that is, be made filler parent granule, and each area's temperature of wherein double screw extruder is：Pre- 150 DEG C of tabetisol, first
200 DEG C of melting zone, the first 205 DEG C of shear at high temperature area, the second 220 DEG C of shear at high temperature area, the second 205 DEG C of warm area of melting, discharging opening
195 DEG C of warm area is melted, screw speed is 450 revs/min.
It is 25 in mass ratio by filler parent granule obtained above and polypropylene：75 mixed after again through melting, extruding
Composite.
Embodiment 6
By 14 parts, 10 parts low density polyethylene (LDPE)s of polypropylene reclaimed material, 6 parts of polypropylene grafted maleic anhydride, antioxidant 0.01
Part, 2.8 parts of lubricant be put into temperature control high-speed mixer and mix 3min, temperature control is at 85 DEG C, rotating speed 650r/min；Then will
In 80 parts of addition high-speed mixers of inorganic mineral filler mica powder, stir while being uniformly added into 2,5- dimethyl -2,5- pair
1.7 parts of (tert-butyl peroxy base) hexane, high mixer rotating speed are controlled in 550r/min, are continued to stir 14min after adding, are premixed
Material；Finally premix is fed in double screw extruder, preheating is after 4 minutes, then through melting, extruding, vacuumizing, it is air-cooled, cut
Grain and dry, i.e., obtained filler parent granule, each area's temperature of wherein double screw extruder are：Pre- 145 DEG C of tabetisol, the first melting zone
195 DEG C, the first 210 DEG C of shear at high temperature area, the second 215 DEG C of shear at high temperature area, the second 200 DEG C of warm area of melting, discharging opening melting temperature
195 DEG C of area, screw speed are 400 revs/min.
It is 25 in mass ratio by filler parent granule obtained above and polypropylene：75 mixed after again through melting, extruding
Composite.
Above-described embodiment 1-6 composites prepared are molded into batten through standard, its performance is as shown in table 1.
Simultaneously by it is existing 230 DEG C melt index is 40~100g/10min in the case of 2.16Kg polypropylene and useless
(moisture content is less than 3% to old polypropylene laundry machine barrel reclaimed materials less than 0.5%, combustion residue, and melt index is in 2.16kg/230
It is 15-60g/10min under the conditions of DEG C) as comparative example, equally it is molded into batten and detects its performance, it is as shown in table 1 below.
The method of testing difference of wherein each physical property is as follows：
Melt flow rate (MFR) is tested according to GB/T 3682-2000
Tensile 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 1834-2008；
Load deformation temperature measures according to GB/T 1634.2-2004；
Table 1：Performance indications：
Polymer-filled master batch is made by the application it can be seen from embodiment in upper table 1 and comparative example result to fill
The composite formed after polypropylene has more preferable rigidity, toughness, intensity compared with commercial polypropylene or polypropylene reclaimed material
And heat resistance, it also has a clear superiority in terms of compatibility, dispersiveness.The regrown material source selected additionally, due to the present invention
It is relatively wide, simple production process, greatly save the cost of raw material.
These embodiments are merely to illustrate the present invention and should not limit the scope of this invention.In addition, reading this hair
After the bright content, those skilled in the art make the change or modification of the various equivalent form of values, these equivalent form of values to the present invention
Also belong to following claims limited range.
Claims (8)
1. one kind polymer-filled master batch made of polypropylene reclaimed material, it is characterised in that：Its by following components by weight
It is prepared：
10~20 parts of polypropylene reclaimed material；
10 ~ 30 parts of low density polyethylene (LDPE)；
2~6 parts of polypropylene grafted maleic anhydride；
75~85 parts of inorganic mineral filler；
Double 1.5~1.7 parts of (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5-；
0.01~0.02 part of antioxidant；
1.5~3 parts of lubricant.
2. polymer-filled master batch according to claim 1, it is characterised in that：After described polypropylene reclaimed material is recovery
The injection grade polypropylene that sorted, cleaning, broken, drying obtain, its moisture content are less than 3% less than 0.5%, combustion residue, melted
It is 15-60g/10min under the conditions of 2.16kg/230 DEG C to melt index.
3. polymer-filled master batch according to claim 1, it is characterised in that：The low density polyethylene (LDPE) melt index exists
2.16kg/230 it is 50 ~ 60 g/10min under the conditions of DEG C.
4. polymer-filled master batch according to claim 1, it is characterised in that：The polypropylene grafted maleic anhydride connects
Branch rate >=1%, weight average molecular weight >=30000.
5. polymer-filled master batch according to claim 1, it is characterised in that：Described inorganic mineral filler is talcum
One or more in powder, calcium carbonate or mica, the mesh of its particle diameter >=3000.
6. polymer-filled master batch according to claim 1, it is characterised in that：The antioxidant be four [β-（3,5- bis- uncles
Butyl -4- hydroxy phenyls）Propionic acid] pentaerythritol ester and 6- (4- hydroxyl -3,5- di-t-butyls phenylamino) just pungent sulphur of -2,4- two
Base -1,3,5- triazines are 1 in mass ratio:4 are compounded.
7. polymer-filled master batch according to claim 1, it is characterised in that：Described lubricant is White Mineral Oil, ethylene
Bis-stearamides and calcium stearate are 2 in mass ratio:1:1 is compounded.
A kind of 8. preparation method of polymer-filled master batch as claimed in claim 1, it is characterised in that：Comprise the following steps：
（1）By the polypropylene reclaimed material of drying process, low density polyethylene (LDPE), polypropylene grafted maleic anhydride, antioxidant, lubrication
Agent is poured into temperature control high-speed mixer by formula rate and mixes 2-3min；The temperature of the mixer is 75 DEG C -90 DEG C, rotating speed is
500-800r/min；
（2）（1）In compound in add inorganic mineral filler, 2,5- dimethyl -2,5- is uniformly added into whipping process
After double (tert-butyl peroxy base) hexanes, continue to be stirred 10-15min, obtain premix；
（3）L/D=44 are put into premix:In 1 double screw extruder, after first preheating 2~4 minutes, then through melting, squeezing
Go out, vacuumize, be air-cooled, pelletizing and drying, i.e., obtained filler parent granule, wherein double screw extruder temperature setting are：Pre- tabetisol 140
~155 DEG C, the first 190~200 DEG C of melting zone, the first 200~210 DEG C of shear at high temperature area, the second shear at high temperature area 210~220
DEG C, the second 200~210 DEG C of warm area of melting, discharging opening 190~200 DEG C of warm area of melting；The rotating speed of process double screw extruder
For 300~500 revs/min.
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| CN201610426021.9A CN107501719A (en) | 2016-06-14 | 2016-06-14 | One kind polymer-filled master batch and preparation method thereof made of polypropylene reclaimed material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109666217A (en) * | 2018-12-25 | 2019-04-23 | 南通新帝克单丝科技股份有限公司 | The method of modifying of polypropylene returns |
| CN110218388A (en) * | 2019-05-27 | 2019-09-10 | 江苏汉德纳米材料科技有限公司 | A kind of antiultraviolet ageing resistance polypropylene master batch and its manufacturing process |
| WO2021028100A1 (en) * | 2019-08-13 | 2021-02-18 | Borealis Ag | Upgraded recycled polyolefin |
| CN113896989A (en) * | 2021-11-30 | 2022-01-07 | 湖南登科材料科技有限公司 | Polyethylene filler and preparation method thereof |
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| CN102070833A (en) * | 2010-12-27 | 2011-05-25 | 金发科技股份有限公司 | Filler masterbatch used for increasing polarity of polypropylene and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109666217A (en) * | 2018-12-25 | 2019-04-23 | 南通新帝克单丝科技股份有限公司 | The method of modifying of polypropylene returns |
| CN110218388A (en) * | 2019-05-27 | 2019-09-10 | 江苏汉德纳米材料科技有限公司 | A kind of antiultraviolet ageing resistance polypropylene master batch and its manufacturing process |
| WO2021028100A1 (en) * | 2019-08-13 | 2021-02-18 | Borealis Ag | Upgraded recycled polyolefin |
| CN114207015A (en) * | 2019-08-13 | 2022-03-18 | 博里利斯股份公司 | Modified recycled polyolefins |
| CN113896989A (en) * | 2021-11-30 | 2022-01-07 | 湖南登科材料科技有限公司 | Polyethylene filler and preparation method thereof |
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Application publication date: 20171222 |
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