CN107722466A - A kind of high-polarity polypropylene composite and preparation method thereof and the application in automobile exterior material - Google Patents
A kind of high-polarity polypropylene composite and preparation method thereof and the application in automobile exterior material Download PDFInfo
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- CN107722466A CN107722466A CN201710887997.0A CN201710887997A CN107722466A CN 107722466 A CN107722466 A CN 107722466A CN 201710887997 A CN201710887997 A CN 201710887997A CN 107722466 A CN107722466 A CN 107722466A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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 discloses a kind of high-polarity polypropylene composite, raw material forms the component for including following percetage by weight：Polypropylene 50%~88%；Toughener 5~15%；Mineral filler 0~30%；Modified polyvinyl chloride 5~10%；Super-branched polyesteramide 1~5%；Auxiliary agent 0.1%~5%.In the present invention, by adding modified polyvinyl chloride and super-branched polyesteramide, the polarity of PP composite material is significantly improved, and keeps excellent mechanical property, can be used as automobile exterior PP Pipe Compound.The preparation method of the high-polarity polypropylene composite, it can be achieved, prepared simply using existing double screw extruder, easy to implement and operation, be easy to industrialized production, possess wide application prospect.
Description
Technical field
The present invention relates to PP composite material field, and in particular to a kind of high-polarity polypropylene composite and its preparation
Method and the application in automobile exterior material.
Background technology
Polypropylene because its have density is small, intensity is high, hardness is big, wear-resisting, resist bending is tired, heat resisting temperature is high, moisture-proof and
Chemical resistance is excellent, the advantages that being easily worked shaping, be cheap is always auto industry and plastics industry focus of attention.Vapour
Car exterior trim material modified polypropylene material, not only needs good impact property, processing characteristics, and also need to good paint
Adhesion property.But polypropylene is a kind of non-polar material, its surface tension is low, is directly molded with unmodified polypropylene material
Into bumper its paint firmness deficiency, the product after spray painting is difficult by the scratch-resistant of domestic and international Zu Ji factories, moisture-proof, water-fast etc.
Experiment.Therefore, in order to increase the paint firmness of bumper, it is necessary to polypropylene is carried out polar-modified, improve article surface pole
Property, strengthen coating adhesion.
The method of conventional raising PP polarity has surface grafting method, surface-crosslinked method, surface coating modified method, addition polarity
Material blending method etc..Method of modifying above can effectively improve the polarity of polypropylene material, but remove and directly add polar material
Outside matter blending method, there is the problem of processing technology complexity or too high modified cost for other method of modifying.
For directly adding polar substances blending modification method, application publication number is the A (Application No. of CN 101717548
200910193704.4) Chinese invention patent application discloses a kind of high-polarity polypropylene material, and as in automobile
Exterior trimming parts, using the component of following percetage by weight：Polypropylene 50%~70%, toughener 14%~20%, polar additive
5%~15%, mineral filler 0%~30%, age resister 0.2%~3%, colouring agent 0~0.5%.The technical scheme be by
Macromolecule polar substances such as TPU (TPU), maleic anhydride inoculated polypropylene, epoxy resin, ethylene acrylic
One or several kinds are with 5%~15% ratio in ester (EEA), ethylene vinyl acetate (EVA), polyetheramine, polybutene polyalcohol
Example is a large amount of to be added in pp material, so as to which high-polarity polypropylene material be made, and is applied in automobile interior exterior decorations.
The and for example A of application publication number CN 101768394 (Application No. 200810189838.4) Chinese invention patent application
A kind of polar modified polymer material and preparation method thereof is disclosed, the parts by weight composition of raw material is：Polypropylene (PP) 50~100
Part, 10~100 parts of LLDPE LLDPEs, 5~20 parts of maleic anhydride inoculated polypropylene, handle through silane coupler
10~40 parts of inorganic material, 2~10 parts of toughener, 0.5 part of 1010 antioxidant.The technical scheme is similarly by macromolecule polarity
Auxiliary agent is largely added in polypropylene material, so as to which high-polarity polypropylene material be made.
However, there are two drawbacks in the way of both the above blending and modifying：1. largely adding macromolecule polar substances can be right
The mechanical property of Pp System causes larger destruction, especially to the Pp System using polypropylene recovery material；2. high score
Sub- Polar adjuvants price general charged is expensive, and so a large amount of addition costs are too high.
The content of the invention
The invention provides a kind of high-polarity polypropylene composite, the composite is provided simultaneously with highly polar and excellent
Mechanical property, and cost is cheap, can be used as automobile exterior PP Pipe Compound.
Concrete technical scheme is as follows：
A kind of high-polarity polypropylene composite, raw material form the component for including following percetage by weight：
In the present invention, the polarity of modified polypropene system is substantially increased by introducing modified polyvinyl chloride, while again
It is used as compatilizer by introducing super-branched polyesteramide.And have been surprisingly found that, super-branched polyesteramide produces with modified polyvinyl chloride
Collaboration, while composite materials property is improved, further improves the polarity of compound system.
Preferably, described polypropylene is high fluidity, High Impact Polypropylene.Its melt index is 15~30g/
10min (230 DEG C, 2.16kg), further preferably, melt index scope are 25~30g/10min.Made from above-mentioned polypropylene
For base-material, excellent mechanical property can be made it have.
Preferably, described toughener is selected from polyethylene octene elastomer (POE).From POE as toughener, energy
Enough mechanical properties for improving high-polarity polypropylene composite of the present invention well.
Preferably, described mineral filler is selected from least one of talcum powder, calcium carbonate, barium sulfate.Above-mentioned ore deposit
Thing filler, cost, increase capacity on the one hand can be reduced, on the other hand, the performance of PP composite material can be improved.
Polyvinyl chloride (PVC) is a kind of polar polymer, has that intensity is high, corrosion resistance is strong, fire-retardant and cheap etc.
Advantage.It is effectively increased the polarity of MODIFIED PP system if appropriate PVC and PP is carried out can is blended and changes so as to greatly improve
The PASS of property PP products.But it is very poor that the significant polarity spectrum of both PP and PVC result in its compatibility.It incite somebody to action both merely
Simply it is blended, the mechanical property of its blend is excessively poor not to reach automobile exterior material performance requirement completely, therefore at this
The direct blend PP of someone and PVC do not prepare automobile exterior material before patent.The polyvinyl chloride used in the present invention is modification
Polyvinyl chloride, its processability of polyvinyl chloride and thermal stability after modified are improved significantly.
Preferably, described modified polyvinyl chloride is by polyvinyl chloride and lead sulfate tribasic (three salt), dibasic phosphorous
Lead plumbate (disalt), stearic acid and paraffin it is blended, plasticizing after obtain.
Further preferably, described modified polyvinyl chloride is made up of following raw material proportioning：PVC/ lead sulfate tribasics (three
Salt)/dibasic lead phosphite (disalt)/stearic acid/paraffin=100:3:2:1:0.4.
Dissaving polymer is a kind of highly branched structure, compact appearance, has a large amount of reactive terminal groups.Due to
These architectural features, their property have larger difference with normal linear polymer, such as：Rheological behavior, utilize power between macromolecular
Effect absorption dyestuff etc..Dissaving polymer is generally generated by polycondensation reaction, and super-branched polyesteramide is by diisopropanolamine
Formed with acid anhydrides polycondensation.By the screening to acid anhydrides and modified end group, a variety of polymer of different nature can be synthesized,
Make it have different dissolubilities, compatibility, interfacial tension etc..
Preferably, described super-branched polyesteramide be first polycondensed into by phthalic anhydride, diisopropanolamine it is hyperbranched
Polyamide, then be prepared through stearic acid esterification C-terminal.Found through experiment, the super-branched polyesteramide of the specific structure
Introduce, the mixed effect of PP/PVC alloys can be improved, make its mechanical property and polarity while be improved, answered with the polypropylene
The product that condensation material is prepared, its mechanical property and PASS can reach automobile exterior material standard., may through analysis
It is due to the presence of fatty acid alkyl chain, the super-branched polyesteramide can be compatible with polypropylene, and the side of polar group one introduced
Face directly increases MODIFIED PP material surface PASS, and the interaction such as hydrogen bond, increase on the other hand can be produced with PVC
The compatibility of PP/PVC systems.
Further preferably, the esterification yield of described its C-terminal of super-branched polyesteramide is 40~60%, such as Dutch DSM
Hybrane B.V. companies Hybrane PS 2550.
Preferably, described auxiliary agent includes at least one of age resister, colouring agent；
Described age resister be selected from suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, matal deactivator,
At least one of benzophenone, benzotriazole light stabilizer.
Described colouring agent can use commercially available prod, can select the species of colouring agent as needed, be generally used for preparing vapour
During car bumper, generally black, colouring agent use carbon black.
Under above-mentioned preferable raw material variety, further preferably, described high-polarity polypropylene composite, raw material composition
Include the component of following percetage by weight：
The invention also discloses the preparation method of described high-polarity polypropylene composite, squeezed using existing twin-screw
Go out machine to can be achieved, prepare simply, easy to implement and operation, be easy to industrialized production.
Comprise the following steps：
By polypropylene, toughener, alternative add ground mineral filler, modified polyvinyl chloride, super-branched polyesteramide, help
Agent is added in blender and mixed, and is then placed in double screw extruder, and extruding pelletization obtains high-polarity polypropylene composite.
Preferably, each raw material is in a mixer with 500~3000rpm mixed at high speed 1~20 minute.
Preferably, the temperature of the melting zone of described double screw extruder is 190 DEG C~220 DEG C.
The invention also discloses application of the described high-polarity polypropylene composite in automobile exterior material.
Compared with prior art, the invention has the advantages that：
The high-polarity polypropylene composite of the present invention, improve the pole of polypropylene material by introducing modified polyvinyl chloride
Property, make it have it is highly polar, so as to strengthen the adhesive force of the material and painting layer.This patent introduces ultrabranching polyamide simultaneously
Bulking agent of the ester as PP/PVC materials, improves compatibility between the two, it is kept excellent mechanical property.And surprisingly send out
Existing, super-branched polyesteramide and modified polyvinyl chloride improve the polarity of PP composite material there occurs mutually cooperateing with
And mechanical property.The mechanical property conservation rate height and paint adhesion for the high-polarity polypropylene composite that the present invention is prepared
Intensity is high, its bumper being molded, and domestic and international auto vendor can be met by painting firmness and every mechanical performance index
It is required that.
The preparation method of the high-polarity polypropylene composite of the present invention, can be real using existing double screw extruder
It is existing, prepare simply, easy to implement and operation, be easy to industrialized production, possess wide application prospect.
Embodiment
Polypropylene is using the model K9026 of Yanshan Petrochemical Co., Ltd production product, melt index 26g/min
(230 DEG C, 2.16kg)；POE uses the product of du pont company's model 8150；Talcum powder uses Suzhou Ze Er chemical products
The talcum powder of Co., Ltd's production；Super-branched polyesteramide is Dutch DSM Hybrane B.V. companies Hybrane PS 2550；
PVC is the SGS-6 of Baoding electrochemical factory；PVC processing aids are commercial grade；Antioxidant 1010 uses the production of German BASF production
Product；Irgasfos 168 is also using the product of German BASF production；Carbon black uses the model MA-100 of MIT's production
Product.
For following comparative example with being used in embodiment as modified PVC, specific modifying process is as follows：
It is made after PVC and PVC dispensings are plastified into 2min in the twin-roll plastic mixing mill of 180 DEG C of roller temperature by following mass ratio；
Each dispensing mass ratio is：
PVC/ lead sulfate tribasics (three salt)/dibasic lead phosphite (disalt)/stearic acid/paraffin=100:3:2:1:
0.4。
Comparative example 1：
By 74 parts by weight of polypropylene, 5 parts by weight POE (8150), 20 parts by weight talcum powder, 0.3 parts by weight antioxidant 1010,
0.2 parts by weight irgasfos 168,0.5 parts by weight of carbon black per, which are added in the super mixer that rotating speed is about 1000rpm, mixes 5 minutes, so
Mixture is put into double screw extruder again afterwards, extruding pelletization obtains at a temperature of 190 DEG C~220 DEG C, obtains the poly- of modification
Acrylic composite.
Comparative example 2：
By 64 parts by weight of polypropylene, 5 parts by weight POE (8150), 20 parts by weight talcum powder, 10 parts of modified PVCs, 0.3 weight
Part antioxidant 1010,0.2 parts by weight irgasfos 168,0.5 parts by weight of carbon black per add the super mixer that rotating speed is about 1000rpm
Middle mixing 5 minutes, is then put into double screw extruder, extruding pelletization obtains at a temperature of 190 DEG C~220 DEG C by mixture again
, obtain modified PP composite material.
Embodiment 1：
By 59 parts by weight of polypropylene, 5 parts by weight POE (8150), 20 parts by weight talcum powder, 10 parts of modified PVCs, 5 parts of over-expenses
Changing polyesteramide, 0.3 parts by weight antioxidant 1010,0.2 parts by weight irgasfos 168,0.5 parts by weight of carbon black per addition rotating speed is about
Mixed 5 minutes in 1000rpm super mixer, mixture is then put into double screw extruder again, at 190 DEG C~220 DEG C
At a temperature of extruding pelletization obtain, obtain modified PP composite material.
Embodiment 2:
By 67 parts by weight of polypropylene, 5 parts by weight POE (8150), 20 parts by weight talcum powder, 5 parts of modified PVCs, 2 parts it is hyperbranched
Polyesteramide, 0.3 parts by weight antioxidant 1010,0.2 parts by weight irgasfos 168,0.5 parts by weight of carbon black per add rotating speed and are about
Mixed 5 minutes in 1000rpm super mixer, mixture is then put into double screw extruder again, at 190 DEG C~220 DEG C
At a temperature of extruding pelletization obtain, obtain modified PP composite material.
Four kinds of material injections that embodiment 1~2 is prepared with comparative example 1~2 scrape embrocation after spraying into bumper with cross
Checking paint firmness.Contrast is found：By the material injection that comparative example 1 provides into bumper, its paint adhesive force it is worst.Cross
Drawn three times after scraping with 3M adhesive tapes are viscous, paint, which has, substantially to come off.And by comparative example 2, embodiment 1 and the material injection of embodiment 2
Into bumper its PASS it is preferable, cross is drawn three times after scraping with 3M adhesive tapes are viscous, and paint does not come off.Use simultaneously
Dyne pen tests dyne index on four kinds of bumper surfaces, and its result is as shown in table 1.
Four kinds of material injections that embodiment 1~2 is prepared with comparative example 1~2 test mechanical property and table into standard batten
Face dyne index, its result are as shown in table 1.
Table 1
Comparative example 2, embodiment 1, embodiment 2 are can be seen that by adding polarity in PP systems from a dyne index for table 1
Polymer modification polyvinyl chloride, its modified compound PP material, its dyne of index significantly improve.Wherein embodiment 1 and implementation
Super-branched polyesteramide is additionally with the addition of in example 2, both further improve dyne index, it was demonstrated that its surface tension further carries
It is high.The mechanical property that can be seen that the material of comparative example 2 from the mechanical property of table 1 will be significantly lower than comparative example 1.Because with it is right
Ratio 1 is compared, and 10 parts of modified PVCs are filled with comparative example 2, due to significant polarity difference between modified PVC and PP, its blend
Mechanical property substantially reduces.5 parts of super-branched polyesteramides are with the addition of in embodiment 1 as PP and the compatilizer of modified PVC, are added
Compound its mechanical property of PP materials after adding is greatly improved, it is already possible to meets the performance of conventional vehicle exterior trim material
It is required that.Reduce the adding proportion of modified PVC and super-branched polyesteramide in example 2, its mechanical property further to
The performance of comparative example 1, and its surface dynes index also obtains higher lifting, the mechanical property for fully meeting automobile exterior material will
With spray painting performance requirement.
Claims (10)
1. a kind of high-polarity polypropylene composite, it is characterised in that raw material forms the component for including following percetage by weight：
2. high-polarity polypropylene composite according to claim 1, it is characterised in that described polypropylene is selected from high flow
Dynamic property, High Impact Polypropylene, melt index is 15~30g/10min.
3. high-polarity polypropylene composite according to claim 1, it is characterised in that described toughener is selected from poly- second
Alkene octene elastomer.
4. high-polarity polypropylene composite according to claim 1, it is characterised in that described mineral filler, which is selected from, to be slided
At least one of stone flour, calcium carbonate, barium sulfate.
5. high-polarity polypropylene composite according to claim 1, it is characterised in that described modified polyvinyl chloride by
Polyvinyl chloride and lead sulfate tribasic (three salt), dibasic lead phosphite (disalt), stearic acid and paraffin is blended, after plasticizing
Arrive.
6. high-polarity polypropylene composite according to claim 1, it is characterised in that described super-branched polyesteramide
Ultrabranching polyamide is first polycondensed into by phthalic anhydride, diisopropanolamine, then is prepared through stearic acid esterification C-terminal.
7. high-polarity polypropylene composite according to claim 1, it is characterised in that described auxiliary agent includes anti-aging
At least one of agent, colouring agent；
Described age resister is selected from suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, matal deactivator, hexichol
At least one of ketone class, benzotriazole light stabilizer.
8. the high-polarity polypropylene composite according to any one of claim 1~7, it is characterised in that raw material composition bag
Include the component of following percetage by weight：
9. a kind of preparation method of high-polarity polypropylene composite according to any one of claim 1~8, its feature exist
In comprising the following steps：
Polypropylene, toughener, alternative ground mineral filler, modified polyvinyl chloride, super-branched polyesteramide, the auxiliary agent of adding are added
Enter and mixed into blender, be then placed in double screw extruder, extruding pelletization obtains high-polarity polypropylene composite.
A kind of 10. high-polarity polypropylene composite according to any one of claim 1~8 answering in automobile exterior material
With.
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| CN201710887997.0A CN107722466B (en) | 2017-09-27 | 2017-09-27 | High-polarity polypropylene composite material, preparation method thereof and application thereof in automobile exterior trim |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651932A (en) * | 2018-12-21 | 2019-04-19 | 六安科瑞达新型材料有限公司 | A kind of high tenacity epoxide powder coating |
| CN110591250A (en) * | 2019-09-12 | 2019-12-20 | 宁波东胜橡胶制品有限公司 | PVC (polyvinyl chloride) foam material for sports shock pad and preparation process thereof |
| CN110951156A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | Polypropylene composite material with high surface tension and excellent comprehensive performance and preparation method thereof |
| CN111087691A (en) * | 2019-12-23 | 2020-05-01 | 上海普利特复合材料股份有限公司 | High-performance high-surface-adhesion polypropylene material suitable for paint spraying and gluing and preparation method thereof |
| CN111690206A (en) * | 2020-07-18 | 2020-09-22 | 万华化学（宁波）有限公司 | Polar polypropylene composite material and preparation method thereof |
| CN112143110A (en) * | 2020-10-16 | 2020-12-29 | 重庆会通科技有限公司 | Polypropylene composition and preparation method and application thereof |
| CN113429670A (en) * | 2021-06-21 | 2021-09-24 | 金旸（厦门）新材料科技有限公司 | Modified polypropylene composite material, preparation method thereof and surface coating method of composite material |
| CN113603962A (en) * | 2021-07-16 | 2021-11-05 | 中广核俊尔(浙江)新材料有限公司 | High-toughness v 0-grade flame-retardant polypropylene composite material for storage battery shell and preparation method thereof |
| CN113789011A (en) * | 2021-08-26 | 2021-12-14 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method and application thereof |
| CN114806004A (en) * | 2021-07-21 | 2022-07-29 | 上海睿聚环保科技有限公司 | Environment-friendly regenerated polypropylene modified special material for automobile exterior trim and preparation method thereof |
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| CN110951156B (en) * | 2018-09-26 | 2022-04-08 | 合肥杰事杰新材料股份有限公司 | Polypropylene composite material with high surface tension and excellent comprehensive performance and preparation method thereof |
| CN110951156A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | Polypropylene composite material with high surface tension and excellent comprehensive performance and preparation method thereof |
| CN109651932A (en) * | 2018-12-21 | 2019-04-19 | 六安科瑞达新型材料有限公司 | A kind of high tenacity epoxide powder coating |
| CN110591250A (en) * | 2019-09-12 | 2019-12-20 | 宁波东胜橡胶制品有限公司 | PVC (polyvinyl chloride) foam material for sports shock pad and preparation process thereof |
| CN111087691A (en) * | 2019-12-23 | 2020-05-01 | 上海普利特复合材料股份有限公司 | High-performance high-surface-adhesion polypropylene material suitable for paint spraying and gluing and preparation method thereof |
| CN111690206A (en) * | 2020-07-18 | 2020-09-22 | 万华化学（宁波）有限公司 | Polar polypropylene composite material and preparation method thereof |
| CN111690206B (en) * | 2020-07-18 | 2022-07-12 | 万华化学(四川)有限公司 | Polar polypropylene composite material and preparation method thereof |
| CN112143110A (en) * | 2020-10-16 | 2020-12-29 | 重庆会通科技有限公司 | Polypropylene composition and preparation method and application thereof |
| CN113429670A (en) * | 2021-06-21 | 2021-09-24 | 金旸（厦门）新材料科技有限公司 | Modified polypropylene composite material, preparation method thereof and surface coating method of composite material |
| CN113603962A (en) * | 2021-07-16 | 2021-11-05 | 中广核俊尔(浙江)新材料有限公司 | High-toughness v 0-grade flame-retardant polypropylene composite material for storage battery shell and preparation method thereof |
| CN114806004A (en) * | 2021-07-21 | 2022-07-29 | 上海睿聚环保科技有限公司 | Environment-friendly regenerated polypropylene modified special material for automobile exterior trim and preparation method thereof |
| CN113789011A (en) * | 2021-08-26 | 2021-12-14 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method and application thereof |
| CN113789011B (en) * | 2021-08-26 | 2023-09-26 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method and application thereof |
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