CN107987400A - A kind of graphene modified polypropene micro foaming composite material and preparation method thereof - Google Patents
A kind of graphene modified polypropene micro foaming composite material and preparation method thereof Download PDFInfo
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- CN107987400A CN107987400A CN201711346394.6A CN201711346394A CN107987400A CN 107987400 A CN107987400 A CN 107987400A CN 201711346394 A CN201711346394 A CN 201711346394A CN 107987400 A CN107987400 A CN 107987400A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The present invention relates to technical field of polymer materials,More particularly to a kind of graphene modified polypropene micro foaming composite material and preparation method thereof,60~65 parts by weight of copolymer polypropylene,1.8~3.5 parts by weight of foaming agent,14~20 parts by weight of talcum powder,15~20 parts by weight of elastomer,2~6 parts by weight of graphene oxide,0.2~0.6 parts by weight of organic amine modifying agent,0.2~0.4 parts by weight of antioxidant,0.5~1 parts by weight of lubricant,Selectable 0~2 parts by weight of auxiliary agent,The present invention carries out graft modification using organic amine modifying agent to graphene oxide,Improve graphene and compatibility in polypropylene,Improve polyacrylic melt strength and mechanical property,And the graphene modified polypropene micro foaming composite material of the present invention is small with density,The characteristics of light weight,It disclosure satisfy that the product requirement of automotive light weight technology,It can be widely applied to automobile door plate,Column,In the components such as centre gangway.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of graphene modified polypropene fretting map composite wood
Material and preparation method thereof.
Background technology
With the exhausted and industrialized process of the energy, automotive light weight technology, new-energy automobile, high-speed railway and novel traffic
Instrument develops towards light weight, safe and environment-friendly direction, and new demand is proposed to high-performance polymer material.Polypropylene is micro-
Expanded material has the features such as light, specific strength is high, heat endurance is high, also with characteristic, the extensive use such as sound insulation and noise reduction is heat-insulated
In fields such as packaging, sports equipment, household electrical appliances, the concern of automotive field is also enjoyed, but polypropylene belongs to semi-crystalline polymer, temperature
Degree drastically declines more than melt viscosity, and general processing temperature is above melting temperature, and viscosity is small can not to hold onto what abscess was grown up
Process, abscess can occur to rupture and steep, go here and there bubble, cause distribution of cells inequality, directly affect the performance of polypropylene fretting map, make
About the application of polypropylene micro-foaming material.Therefore, how to improve the melt strength of polypropylene material, control its foaming process into
For the direction of researcher's concern.A kind of effective method is addition nano material to improve polyacrylic melt strength,
Also strengthen its mechanical property at the same time, improve polyacrylic foam performance, widen the application range of polypropylene micro-foaming material.Graphite
Alkene is the two-dimension nano materials being made of one layer of carbon atom, has high-modulus, high-specific surface area, chemical stability are highly conductive to lead
The features such as hot, be the novel nano-material for having now been found that performance is most strong, is referred to as " king of new material ", under low content filling
Performance with regard to polymer can be increased substantially, but graphene size is small, and specific surface area is big, is easy to reunite, causes polymeric matrix
Middle poor dispersion, can influence the mechanical property and foam performance of polymer composites on the contrary.
The content of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of graphene modified polypropene fretting map composite wood
Material, it has excellent mechanical property, and abscess is fine and smooth uniformly in composite material.
The present invention also provides a kind of preparation method of graphene modified polypropene micro foaming composite material, it, which has, prepares work
Skill is simple, is adapted to industrialized production.
To achieve these goals, the present invention provides a kind of graphene modified polypropene micro foaming composite material, by raw material
Composition is made, and the feedstock composition includes：
The present invention also provides a kind of preparation method of the graphene modified polypropene micro foaming composite material, including it is following
Step：
(1) by graphene oxide and organic amine modifying agent in acetone after mixing, 24 are stirred at 40~50 DEG C~
48h, then centrifuges, washs, is dry, obtaining organically-modified graphene oxide；
(2) organically-modified graphene oxide, copolymer polypropylene, talcum powder, elastomer, antioxidant, lubricant and auxiliary agent mix
After closing uniformly, after putting into double screw extruder, melting extrusion is crossed, is granulated, PP composite material is made；
(3) PP composite material and foaming agent are added into injection molding machine hopper after mixing, carry out twice-die-opening injection,
Obtain graphene modified polypropene micro foaming composite material.
Through the above technical solutions, the present invention has following technique effect：
(1) present invention carries out graft modification using organic amine modifying agent to graphene oxide, draws in surface of graphene oxide
Enter lipophilic group, improve graphene and polyacrylic compatibility, while improve polyacrylic melt strength；Through graft modification
Graphene oxide afterwards in matrix, can be occurred entanglement and crosslink density with polypropylene molecular chain, carried with nano-size dispersion
The high mechanical property of polypropylene matrix.
(2) graphene oxide potentially acts as heterogeneous nucleation point, increases distribution of cells density, and the matrix of high fondant-strength is effective
Cell growth is supported, suppresses cell growth and rupture, obtains the fine and smooth uniform micro-foaming material of abscess.
(3) density of graphene modified polypropene micro foaming composite material of the invention is small, light weight, disclosure satisfy that automobile
Light-weighted product requirement, can be widely applied in the components such as automobile door plate, column, centre gangway.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of graphene modified polypropene micro foaming composite material, it is made of feedstock composition, it is described
Feedstock composition includes：
Under optimum condition, the melt flow rate (MFR) (MI) of the copolymer polypropylene (copolymerization PP) is 30~100g/10min.
In order to optimize the mechanical property of the graphene modified polypropene micro foaming composite material, under optimum condition, institute
It is linear ethylene-octene copolymer (POE) to state elastomer；It is further preferred that the melt flow rate (MFR) of the elastomer for 5~
30g/10min。
The present invention carries out graft modification using organic amine modifying agent to graphene oxide, and parent is introduced in surface of graphene oxide
Oil base group, improves graphene and compatibility in polypropylene, while improves polyacrylic melt strength；After graft modification
Graphene oxide in matrix, can be occurred entanglement and crosslink density with polypropylene molecular chain, improved with nano-size dispersion
The mechanical property of polypropylene matrix；Under optimum condition, the organic amine modifying agent be selected from octadecylamine, octadecyldiethanol amine and
At least one of N- octadecyldiethanol amines.
Talcum powder can reduce polypropylene shrinking percentage, improve polyacrylic heat resistance, under optimum condition, the talcum powder
Particle diameter is 0.3 μm~2 μm.
In order to further optimize the inoxidizability of polypropylene micro foaming composite material, under optimum condition, the antioxidant choosing
From at least one of Hinered phenols antioxidant, thiosulfates kind antioxidant and phosphite ester kind antioxidant, further preferably
, the Hinered phenols antioxidant is antioxidant 1010, and the thiosulfates kind antioxidant is anti-oxidant DLTP, the phosphorous
Acid esters kind antioxidant is irgasfos 168.
In order to simplify the expressing technique of polypropylene micro foaming composite material, also added in the present invention in copolymer polypropylene
Lubricant, under optimum condition, the lubricant is Tissuemat E, calcium stearate, zinc stearate, lignite wax and pentaerythrite are stearic
At least one of acid esters.
In order to further improve the comprehensive performance of polypropylene micro foaming composite material, the present invention also adds in the composite
Auxiliary agent, the auxiliary agent in UV absorbers, light stabilizer, finishing agent, antistatic additive and the colouring agent at least
One kind, it is further preferred that the ultra-violet absorber is selected from least one of UV-9, UV-531 and UVP-327；The light
Stabilizer is selected from least one of light stabilizer 292, light stabilizer 622, light stabilizer 770 and light stabilizer 944；The table
The one kind of face brightener in erucyl amide, glycerin monostearate, oleamide；The antistatic additive is selected from polyether ester acyl
At least one of amine, epoxypropane copolymerization thing and ethylene oxide；The colouring agent is selected from carbon black, lemon yellow, indigo, phthalocyanine
It is at least one of green.
In order to reduce harm of the foaming agent to environment, under optimum condition, the present invention uses environmentally protective micro-foaming material,
For example, the chemical foaming agent be foaming agent using LDPE as carrier, sodium acid carbonate parcel LDPE carrier insides.
The present invention also provides a kind of preparation method of graphene modified polypropene micro foaming composite material, including following step
Suddenly：
(1) by graphene oxide and organic amine modifying agent in acetone after mixing, 24 are stirred at 40~50 DEG C~
48h, then centrifuges, washs, is dry, obtaining organically-modified graphene oxide；
(2) organically-modified graphene oxide, copolymer polypropylene, talcum powder, elastomer, antioxidant, lubricant and auxiliary agent mix
After closing uniformly, after putting into double screw extruder, melting extrusion is crossed, is granulated, PP composite material is made；
(3) PP composite material and foaming agent are added into injection molding machine hopper after mixing, carry out twice-die-opening injection,
Obtain graphene modified polypropene micro foaming composite material.
Under the conditions of, according to the invention it is preferred to, in step (2), the technique of the melting extrusion is：Extrusion temperature is 180
~200 DEG C, screw speed is 350~400r/min, and vacuum is -0.06~-0.08MPa.
Under optimum condition, in step (3), the temperature of the injection molding is 190~210 DEG C.
The present invention will be described in detail by way of examples below.In following embodiments, copolymer polypropylene (BX3920)
Purchased from South Korea SK, copolymer polypropylene (M60RHC) is purchased from Zhenghai refinery, and copolymer polypropylene (311MK40T) is purchased from middle husky Tianjin, hair
Infusion (EE405F) is purchased from chemical conversion industry Co., Ltd. of Japanese Yonghe County, and POE 8407, POE 8137 and POE 8200 are purchased from the U.S.
DOW, graphene oxide are purchased from Beijing English cycolin.
Embodiment 1
A kind of graphene modified polypropene micro foaming composite material, is made of the material of following parts by weight：
(1) by 2 parts by weight graphene oxides and 0.2 parts by weight octadecylamine in 200mL acetone after mixing, at 40 DEG C
Lower stirring 48h, then with deionized water centrifuge washing 3 times, is then dried in vacuo 24h at 60 DEG C, obtains organically-modified oxidation
Graphene；
(2) organically-modified graphene oxide, 60 parts by weight copolymer polypropylene, 18 parts by weight talcum powder, 20 parts by weight POE
8407th, 0.1 parts by weight antioxidant 1010,0.1 parts by weight irgasfos 168 and 0.5 parts by weight of calcium stearate after mixing, are put into
After parallel dual-screw extruding machine, melting extrusion is crossed, is granulated, PP composite material is made；The extrusion temperature of wherein extruder is
180 DEG C, screw speed 350r/min, vacuum is -0.06MPa；
(3) PP composite material and 1.8 parts by weight of blowing agent EE405F are added into injection molding machine hopper after mixing, into
Row twice-die-opening is molded, and injection temperature is 210 DEG C, obtains graphene modified polypropene micro foaming composite material.
Embodiment 2
A kind of graphene modified polypropene micro foaming composite material, is made of the material of following parts by weight：
The preparation method of the graphene modified polypropene micro foaming composite material, step are as follows：
(1) 4 parts by weight graphene oxides are mixed with 0.4 parts by weight octadecyldiethanol amine in 300mL acetone
After even, 24h is stirred at 50 DEG C, then with deionized water centrifuge washing 3 times, then 48h is dried in vacuo at 40 DEG C, is had
Machine modified graphene oxide；
(2) organically-modified graphene oxide, 60 parts by weight copolymer polypropylene 311MK40T, 18 parts by weight talcum powder, 20 weights
Measure part POE 8137,0.15 parts by weight antioxidant 1010,0.15 parts by weight irgasfos 168 and the mixing of 0.5 weight account polyethylene wax
After uniformly, after putting into parallel dual-screw extruding machine, melting extrusion is crossed, is granulated, PP composite material is made；Wherein extruder
Extrusion temperature is 200 DEG C, screw speed 400r/min, and vacuum is -0.08MPa；
(3) PP composite material and 3.5 parts by weight of blowing agent EE405F are added into injection molding machine hopper after mixing, into
Row twice-die-opening is molded, and injection temperature is 190 DEG C, obtains graphene modified polypropene micro foaming composite material.
Embodiment 3
A kind of graphene modified polypropene micro foaming composite material, is made of the material of following parts by weight：
The preparation method of the graphene modified polypropene micro foaming composite material, step are as follows：
(1) 6 parts by weight graphene oxides are mixed with 0.6 parts by weight octadecyldiethanol amine in 400mL acetone
After even, 48h is stirred at 50 DEG C, then with deionized water centrifuge washing 3 times, then 36h is dried in vacuo at 50 DEG C, is had
Machine modified graphene oxide；
(2) organically-modified graphene oxide, 65 parts by weight copolymer polypropylene M60RHC, 16 parts by weight talcum powder, 15 weight
Part POE 8200,0.15 parts by weight antioxidant 1010,0.15 parts by weight antioxidant DSTP, 0.75 parts by weight of calcium stearate, 0.5 weight
Measure part UVP-327,0.5 parts by weight light stabilizer 622 and 1 parts by weight phthalocyanine green after mixing, put into Co rotating Twin Screw Extrusion
After machine, melting extrusion is crossed, is granulated, PP composite material is made；Wherein the extrusion temperature of extruder is 190 DEG C, screw speed
For 400r/min, vacuum is -0.08MPa；
(3) PP composite material and 2 parts by weight of blowing agent EE405F are added into injection molding machine hopper after mixing, carried out
Twice-die-opening is molded, and injection temperature is 200 DEG C, obtains graphene modified polypropene micro foaming composite material.
Embodiment 4
A kind of graphene modified polypropene micro foaming composite material, is made of the material of following parts by weight：
The preparation method of the graphene modified polypropene micro foaming composite material is the same as embodiment 3.
Comparative example 1
According to the method for embodiment 3, the difference is that, graft modification is not carried out to graphene oxide and (do not contain step
(1))。
Comparative example 2
According to the method for embodiment 3, the difference is that, do not add graphene.
Comparative example 3
According to the method for embodiment 3, unlike, do not add talcum powder,
Test：By the main physical index root of PP composite material made from above-described embodiment 1~4 and comparative example 1~3
According to coherent detection standard testing, its apparent density, tensile strength, Izod notched impact strength, bending strength, bending modulus
Examination criteria is as shown in table 1 with testing result.
Table 1：The performance table of PP composite material made from embodiment 1-4 and comparative example 1~3
It can be obtained by table 1：By adding organically-modified graphene oxide in polypropylene micro foaming composite material,
Slight polyacrylic stretching, impact strength and bending modulus can be significantly improved, improves gas in polypropylene micro foaming composite material
The uniformity in hole, reduces the density of polypropylene micro foaming composite material, meets automotive light weight technology, the use of new-energy automobile is wanted
Ask, can be widely applied to the components such as automobile door plate, column, centre gangway.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of graphene modified polypropene micro foaming composite material, it is characterised in that be made of feedstock composition, the raw material
Composition includes：
2. graphene modified polypropene micro foaming composite material according to claim 1, wherein, the copolymer polypropylene
Melt flow rate (MFR) is 30~100g/10min.
3. graphene modified polypropene micro foaming composite material according to claim 1, wherein, the elastomer is linear
Ethylene-octene copolymer；The melt flow rate (MFR) of the elastomer is 5~30g/10min.
4. graphene modified polypropene micro foaming composite material according to claim 1, wherein, the organic amine modifying agent
Selected from least one of octadecylamine, octadecyldiethanol amine and N- octadecyldiethanol amines.
5. graphene modified polypropene micro foaming composite material according to claim 1, wherein, the particle diameter of the talcum powder
For 0.3 μm~2 μm.
6. graphene modified polypropene micro foaming composite material according to claim 1, wherein, the antioxidant be selected from by
Hinder at least one of phenolic antioxidant, thiosulfates kind antioxidant and phosphite ester kind antioxidant.
7. graphene modified polypropene micro foaming composite material according to claim 1, wherein, the auxiliary agent is selected from ultraviolet
Light absorber, finishing agent, light stabilizer, at least one of antistatic additive and colouring agent.
8. the preparation side of the graphene modified polypropene micro foaming composite material according to any one in claim 1~7
Method, it is characterised in that comprise the following steps：
(1) by graphene oxide and organic amine modifying agent in acetone after mixing, 24~48h is stirred at 40~50 DEG C,
Then centrifuge, wash, is dry, obtaining organically-modified graphene oxide；
(2) organically-modified graphene oxide, copolymer polypropylene, talcum powder, elastomer, antioxidant, lubricant and auxiliary agent mixing are equal
After even, after putting into double screw extruder, melting extrusion is crossed, is granulated, PP composite material is made；
(3) PP composite material and foaming agent are added into injection molding machine hopper after mixing, carries out twice-die-opening injection, obtain
Graphene modified polypropene micro foaming composite material.
9. the preparation method of graphene modified polypropene micro foaming composite material according to claim 8, wherein, in step
(2) in, the technique of the melting extrusion is：Extrusion temperature is 180~200 DEG C, and screw speed is 350~400r/min, vacuum
Spend for -0.06~-0.08MPa.
10. the preparation method of graphene modified polypropene micro foaming composite material according to claim 9, wherein, it is described
The temperature of injection molding is 190~210 DEG C.
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| CN109161092A (en) * | 2018-06-30 | 2019-01-08 | 杭州高烯科技有限公司 | A kind of graphene-expanded polypropylene composite material and preparation method |
| CN110437539A (en) * | 2019-09-02 | 2019-11-12 | 万华化学（宁波）有限公司 | A kind of modified chlorinated graphene and high melt strength polypropylene material |
| CN111004442A (en) * | 2019-12-23 | 2020-04-14 | 广东道生科技股份有限公司 | High-strength low-specific gravity foamed polypropylene material using plastic instead of steel and preparation method thereof |
| CN111019240A (en) * | 2019-12-11 | 2020-04-17 | 万华化学（宁波）有限公司 | Polypropylene composite material for injection molding foaming and preparation method thereof |
| CN111057314A (en) * | 2019-12-12 | 2020-04-24 | 会通新材料股份有限公司 | Polypropylene composition with high surface tension and preparation method thereof |
| CN111171456A (en) * | 2018-11-13 | 2020-05-19 | 联泓(江苏)新材料研究院有限公司 | Polypropylene composite material and preparation method thereof |
| CN111574241A (en) * | 2020-05-15 | 2020-08-25 | 江苏银辉生态科技有限公司 | HKS modified polypropylene heat preservation sound insulation board |
| CN113831638A (en) * | 2021-09-16 | 2021-12-24 | 湖北龙辰科技股份有限公司 | Anti-aging BOPP film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109161092A (en) * | 2018-06-30 | 2019-01-08 | 杭州高烯科技有限公司 | A kind of graphene-expanded polypropylene composite material and preparation method |
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| CN110437539B (en) * | 2019-09-02 | 2021-12-10 | 万华化学（宁波）有限公司 | Modified chlorinated graphene and high-melt-strength polypropylene material |
| CN111019240A (en) * | 2019-12-11 | 2020-04-17 | 万华化学（宁波）有限公司 | Polypropylene composite material for injection molding foaming and preparation method thereof |
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| CN111057314A (en) * | 2019-12-12 | 2020-04-24 | 会通新材料股份有限公司 | Polypropylene composition with high surface tension and preparation method thereof |
| CN111004442A (en) * | 2019-12-23 | 2020-04-14 | 广东道生科技股份有限公司 | High-strength low-specific gravity foamed polypropylene material using plastic instead of steel and preparation method thereof |
| CN111574241A (en) * | 2020-05-15 | 2020-08-25 | 江苏银辉生态科技有限公司 | HKS modified polypropylene heat preservation sound insulation board |
| CN113831638A (en) * | 2021-09-16 | 2021-12-24 | 湖北龙辰科技股份有限公司 | Anti-aging BOPP film and preparation method and application thereof |
| CN113831638B (en) * | 2021-09-16 | 2023-01-20 | 湖北龙辰科技股份有限公司 | Anti-aging BOPP film and preparation method and application thereof |
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Application publication date: 20180504 |