CN101759911A - Polypropylene composite material with excellent rigid-tough balance and preparation method thereof - Google Patents
Polypropylene composite material with excellent rigid-tough balance and preparation method thereof Download PDFInfo
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- CN101759911A CN101759911A CN200810203127A CN200810203127A CN101759911A CN 101759911 A CN101759911 A CN 101759911A CN 200810203127 A CN200810203127 A CN 200810203127A CN 200810203127 A CN200810203127 A CN 200810203127A CN 101759911 A CN101759911 A CN 101759911A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract
The invention discloses a polypropylene composite material with excellent rigid-tough balance, belonging to the modification and processing field of polymers. The polypropylene composite material is formulated by the following raw materials by weight percent: 55-95% of polypropylene; 3-30% of wollastonite; 0-10% of other inorganic filler; 0-20% of toughening agent POE; 0.1-2% of antioxidant; and 0-5.0% of other auxiliaries; according to the method, the polypropylene composite material with excellent rigid-tough balance is prepared by adding an inorganic filler, capable of effectively compensating for the lost rigidity owing to toughening, to a fundamental formula aiming at toughening the polypropylene composite material.
Description
Technical field
The present invention relates to a kind of the have polypropylene composite material of excellent rigid-tough balance and the preparation method of this matrix material thereof, more particularly add the rigidity of being sacrificed when a kind of mineral filler wollastonite remedies material by elastic body toughening by the mode of side direction feeding, thereby make material obtain excellent rigid-tough balance, belong to polymer modification and manufacture field.
Background technology
Polypropylene is one of general-purpose plastics of present consumption maximum, because having density, little ((0.89-0.91g/cm3), price are low, nontoxicity, corrosion-resistant, advantage such as electrical insulation capability is good, the transparency and processibility are good, are widely used in industries such as chemical industry, machinery, electric power, transportation.The wherein application of polypropylene material on automobile become one of main direction of studying of Domestic Automotive Industry component production domesticization.But the shortcoming of polypropylene material is poor toughness, wears no resistance, and fragility is bigger during low temperature, as the structural part material, has many deficiencies, has limited the further expansion of its Application Areas.At present, successful plastic toughening mostly with elastomerics as toughner, and be scattered in by rights in the plastic substrate to reach the purpose of toughening modifying, but some performances of material such as Young's modulus, rigidity, softening temperature, fluidity of molten etc. are significantly descended, and price also increases to some extent simultaneously.And with inorganic substance filled polypropylenes such as talcum powder, lime carbonate, polynites, can improve its dimensional stability, thermotolerance, rigidity, and can reduce material cost, strengthen simultaneously and toughness reinforcing contradiction but can't solve plastics.
Modern society and science and technology have proposed increasingly extensive and harsh requirement to polymer materials, both required functional cheap again, not only high temperature resistant but also easily machine-shaping, the toughness of existing brilliance has higher modulus of elasticity etc. again.Therefore for diversified service requirements, polypropylene is by improving its intensity with the nano material blend and toughness is a kind of novel method that development in recent years is got up.But the crystal grain of nano material is little, table and characteristics such as curvature is big, the atomicity of lack of alignment shared percentage ratio of surface atom in the crystalline material so be present in the crystal grain table, and also have various defectives at same nanomorphic intragranular, it is very easily reunited at normal temperatures.With regard to filled polypropylene, because polypropylene is non-polar polymer, and that nanoparticle is compared polarity difference with it is very big, and consistency is poor, and the nano-particles filled polypropylene through special processing does not seldom arrive the high performance structural material yet.
At this problem, Liu Xijun, Wang Huimin, Li Qingshan etc. are that mentioning with a kind of small-entity polypropylene in the CN1361198A patent is base-material in patent publication No., by with co-polypropylene, polyolefin elastomer, wollastonite and other auxiliary agent blending and modifyings, the PP Pipe Compound that is particularly suitable for bumper and door-plate that makes.But take the reinforced mode of blend to fill wollastonite in the course of processing, the shearing of screw rod causes the destruction of wollastonite needle-like form easily, has caused the loss of performance to a certain extent.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, a kind of polypropylene composite material with excellent rigid-tough balance is provided, and the preparation method that in actual production, can improve the polypropylene composite material rigid-tough balance simply and effectively.
The present invention is by adding the rigidity of being sacrificed when a kind of mineral filler wollastonite remedies material by elastic body toughening by the mode of side direction feeding in polypropylene composite material, thereby makes material obtain excellent rigid-tough balance.
In order to improve the rigid-tough balance of polypropylene composite material, technical scheme of the present invention is to add a kind of mineral filler wollastonite in the basic components of polypropylene material, the rigidity that this wollastonite can be fabulous is sacrificed when remedying material by elastic body toughening.A kind of polypropylene composite material with excellent rigid-tough balance is mixed with by following raw materials by weight percent:
Polypropylene 55～95%
Wollastonite 3～30%
Other mineral fillers 0～10%
Toughner POE 0～20%
Oxidation inhibitor 0.1～2%
Other auxiliary agents 0～5.0%
In the polypropylene composite material system that the present invention was suitable for, described polypropylene is that melt flow rate (MFR) is 2～60g/10min (test condition: 230 ℃ * 2.16kg) homo-polypropylene or block copolymerization propylene, wherein the comonomer of block copolymerization propylene is common is ethene, its content is in the scope of 4～10mol%, the degree of crystallinity of homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%; Described other mineral fillers are talcum powder, lime carbonate, mica, barium sulfate or their composition, and its particle size range is 1～10 micron; Described toughner POE (polyolefin elastomer) is linear ethylene-octene copolymer, and density is 0.86～0.90g/cm
3, melting index is 0.5～20g/10min (test condition: 190 ℃ * 2.16kg); Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant can select for use hindered phenol or thioesters kind antioxidant as 3114,1010, DSTP (Negonox) wherein one or more; Auxiliary anti-oxidant can select for use the phosphorite kind antioxidant as 618,168 etc.Described other additives comprise one or more of shades of colour additive, photostabilizer, various ester class or fatty acid lubricant etc.
Wollastonite of the present invention is a kind of mineral of needle-like or needle-like crystalline form of white, and its length-to-diameter ratio scope is 20: 1 to 3: 1.This specific character makes its fabulous rigidity of being sacrificed when having remedied material by elastic body toughening.
Other additives of the present invention comprise shades of colour additive, various ester class or fatty acid lubricant etc.
Above-mentioned polypropylene composite material with excellent rigid-tough balance, its preparation method is as described below:
(1) takes by weighing raw material by weight ratio;
(2) polypropylene, other mineral fillers (not comprising wollastonite), toughner, oxidation inhibitor, photostabilizer or other additives were done in super mixer mixed 3～5 minutes;
(3) raw materials mixed is placed dual-screw-stem machine, the mode by the side direction feeding adds the mineral filler wollastonite, through melt extruding, and granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
The present invention adds in the basic components of toughened polypropylene composite a kind ofly can effectively remedy toughness reinforcing inflexible mineral filler of sacrificing, thereby prepares the polypropylene composite material with excellent rigid-tough balance.
Advantage of the present invention is:
Thereby the use properties of the matrix material that the rigidity of being sacrificed when 1, the present invention remedies material by elastic body toughening by the mineral filler wollastonite that adds a kind of needle-like crystalline form improves greatly.
2, the present invention adopts the mode of side direction feeding to add wollastonite, rather than takes traditional blend feed way, has avoided the brute force shearing of screw rod to cause wollastonite needle-like form to be destroyed, and has caused the material loss of energy.Make polypropylene compound material prepared when improving rigidity of material, the toughness of material is unaffected substantially.
3, the method preparation technology who improves polypropylene composite material rigid-tough balance energy that the present invention proposes is simple, production cost is low.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and Comparative Examples composite-material formula, polypropylene is that melt flow rate (MFR) is 2～60g/10min (test condition: 230 ℃ * 2.16kg) homo-polypropylene and block copolymerization propylene, wherein the comonomer of block copolymerization propylene is common is ethene, and its content is in the scope of 4～10mol%; The degree of crystallinity of homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%.Talcous particle size range is 10 microns.Toughner POE is linear ethylene-octene copolymer that E.I.Du Pont Company produces, and density is 0.86～0.90g/cm
3, melting index is 0.5～20g/10min (test condition: 190 ℃ * 2.16kg).Wollastonite is the mineral of metal-free needle-like of a kind of white or needle-like crystalline form, and its length-to-diameter ratio scope is 20: 1 to 3: 1.Described primary antioxidant is the DSTP that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester, and Ciba company produce 3114, trade names are Irganox 3114, and chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid.Auxiliary anti-oxidant is 168 of Ciba company product, and trade names are Irgafos 168, and chemical name is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Described photostabilizer is 944 of Ciba company product, and chemical name is poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] }, and Ciba company produce 770, chemical name be pairs (2,2,6, the 6-tetramethyl-piperidyl) sebate.Comprise shades of colour additive, various ester class or fatty acid lubricant etc. in addition.
Polypropylene, other mineral fillers (not comprising wollastonite), toughner, oxidation inhibitor, photostabilizer or other additives were done in super mixer mixed 3～5 minutes; Raw materials mixed is placed dual-screw-stem machine, and the mode by the side direction feeding adds the mineral filler wollastonite, through melt extruding, and granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 90～100 ℃ convection oven dry 2～3 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection moulding machine.
The tensile property test is undertaken by ISO 527-2, and specimen size is 170*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 80*10*4mm, and notch depth is 1/3rd of a sample thickness; Heat-drawn wire is undertaken by ISO 75, and specimen size is 120*10*3.0mm, and load is 0.455MPa.
Comprehensive mechanical performance is passed judgment on by the numerical value of shock strength, notched Izod impact strength, tensile strength, flexural strength and the modulus in flexure of test gained.Example formulations and every The performance test results be Lie Gebiao as follows:
Table 1 embodiment 1-3 and Comparative Examples 1-3 material prescription table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Polypropylene, weight % | ??84.6 | ??79.6 | ??71.6 | ??84.6 | ??79.6 | ??71.6 |
| Wollastonite, weight % | ??15 | ??20 | ??18 | ??- | ??- | ??- |
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Talcum powder, weight % | ??- | ??- | ??- | ??15 | ??20 | ??18 |
| Toughner POE, weight % | ??- | ??- | ??10 | ??- | ??- | ??10 |
| Antioxidant 3114, weight % | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
| Oxidation inhibitor DSTP weight % | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Oxidation inhibitor 168, weight % | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
Test result of each prescription is referring to table 2:
Table 2 embodiment 1-3 and Comparative Examples 1-3 test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Melting index (g/10min) | ??12 | ??12.6 | ??8.5 | ??11 | ??11.7 | ??8.6 |
| Notched Izod impact strength (kJ/m 2) | ??9 | ??7.2 | ??19 | ??10.5 | ??8 | ??20.8 |
| Tensile strength (MPa) | ??23.1 | ??22.4 | ??22 | ??23.4 | ??22.3 | ??21.5 |
| Elongation at break (%) | ??7.2 | ??6.4 | ??8.8 | ??8 | ??6.2 | ??9.2 |
| Flexural strength (MPa) | ??41.3 | ??44.6 | ??36 | ??41.3 | ??40.9 | ??35 |
| Modulus in flexure (MPa) | ??1743 | ??1983 | ??1550 | ??1520 | ??1792 | ??1320 |
| Heat-drawn wire (℃) | ??108 | ??110 | ??102 | ??105 | ??108 | ??98.6 |
Table 3 embodiment 4-6 and Comparative Examples 4-6 material prescription table
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | |
| Polypropylene, weight % | ??74.6 | ??69.6 | ??59.6 | ??74.6 | ??69.6 | ??59.6 |
| Wollastonite, weight % | ??25 | ??30 | ??30 | ??- | ??- | ??- |
| Talcum powder, weight % | ??- | ??- | ??- | ??25 | ??30 | ??30 |
| Toughner POE, weight % | ??- | ??- | ??10 | ??- | ??- | ??10 |
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | |
| Antioxidant 3114, weight % | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
| Oxidation inhibitor DSTP weight % | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Oxidation inhibitor 168, weight % | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
Test result of each prescription is referring to table 4:
Table 4 embodiment 4-6 and Comparative Examples 4-6 test result
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | |
| Melting index (g/10min) | ??10.8 | ??10.5 | ??7.4 | ??11 | ??11.7 | ??8.6 |
| Notched Izod impact strength (kJ/m 2) | ??7.6 | ??5.4 | ??14.3 | ??6.9 | ??5.8 | ??12.6 |
| Tensile strength (MPa) | ??28.2 | ??29.5 | ??26.1 | ??27.6 | ??29.4 | ??24.8 |
| Elongation at break (%) | ??5.1 | ??4.4 | ??7.7 | ??5.5 | ??4.2 | ??7.3 |
| Flexural strength (MPa) | ??46.8 | ??48.7 | ??41.2 | ??42.3 | ??44.9 | ??36.8 |
| Modulus in flexure (MPa) | ??2148 | ??2467 | ??1982 | ??1931 | ??2158 | ??1535 |
| Heat-drawn wire (℃) | ??116 | ??122 | ??110 | ??109 | ??117 | ??104 |
From the contrast of the contrast of embodiment 1,2,4,5 and Comparative Examples 1,2,4,5 and embodiment 3,6 and Comparative Examples 3,6 as can be seen, no matter be the binary system of polypropylene and mineral filler or toughner arranged and the polypropylene three-component compound system of mineral filler that the mineral filler wollastonite is helpful for the rigidity and the thermotolerance that improve matrix material.Wherein in polypropylene and the mineral filler binary system, under the situation of same filling umber, the wollastonite infill system is compared the talcum powder infill system has obviously improved material when keeping toughness of material rigidity.The rigidity of being sacrificed when also wollastonite can remedy material well by elastic body toughening as can be seen from the material mechanical performance contrast of embodiment 3,6 and Comparative Examples 3,6 simultaneously, make material have excellent rigid-tough balance, greatly improved the use value of material.
Claims (10)
1. polypropylene composite material with excellent rigid-tough balance, formulated by following raw materials by weight percent:
Polypropylene 55～95%
Wollastonite 3～30%
Other mineral fillers 0～10%
Toughner POE 0～20%
Oxidation inhibitor 0.1～2%
Other auxiliary agents 0～5.0%.
2. the polypropylene composite material with excellent rigid-tough balance according to claim 1 is characterized in that: described polypropylene is that melt flow rate (MFR) is homo-polypropylene or the block copolymerization propylene of 2～60g/10min.
3. the polypropylene composite material with excellent rigid-tough balance according to claim 2 is characterized in that: the comonomer of described block copolymerization propylene is an ethene, and its content is 4～10mol%.
4. the polypropylene composite material with excellent rigid-tough balance according to claim 2 is characterized in that: the degree of crystallinity of described homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%.
5. the polypropylene composite material with excellent rigid-tough balance according to claim 1 is characterized in that: described other mineral fillers are talcum powder, lime carbonate, mica, barium sulfate or their mixture, and its particle size range is 1～10 micron.
6. the polypropylene composite material with excellent rigid-tough balance according to claim 1 is characterized in that: described toughner POE is linear ethylene-octene copolymer, and density is 0.86～0.90g/cm
3, melting index is 0.5～20g/10min.
7. the polypropylene composite material with excellent rigid-tough balance according to claim 1 is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is selected from hindered phenol or thioesters kind antioxidant; Auxiliary anti-oxidant is selected from the phosphorite kind antioxidant.
8. the polypropylene composite material with excellent rigid-tough balance according to claim 7 is characterized in that: described primary antioxidant be 3114,1010 and DSTP in one or more, auxiliary anti-oxidant is 618 and 168.
9. the polypropylene composite material with excellent rigid-tough balance according to claim 1 is characterized in that: described other additives comprise one or more of shades of colour additive, photostabilizer, various ester class or fatty acid lubricant etc.
10. aforesaid right requires any one described preparation method with polypropylene composite material of excellent rigid-tough balance of 1-9, and its concrete steps are: 1) take by weighing raw material by weight ratio;
(2) except that wollastonite, polypropylene, other mineral fillers, toughner, oxidation inhibitor, photostabilizer or other additives were done in super mixer mixed 3～5 minutes;
(3) raw materials mixed is placed dual-screw-stem machine, the mode by the side direction feeding adds the mineral filler wollastonite, through melt extruding, and granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102311583A (en) * | 2011-07-15 | 2012-01-11 | 上海俊尔新材料有限公司 | Rigidity-toughness balanced polypropylene |
| CN102514330A (en) * | 2011-12-08 | 2012-06-27 | 上海普利特复合材料股份有限公司 | PVC cladded polypropylene micro-foamed plastic and its preparation technology |
| CN102532776A (en) * | 2011-12-21 | 2012-07-04 | 中国石油化工股份有限公司 | Low-smell rigid-tough high-performance polypropylene composite material and preparation method thereof |
| CN102532692A (en) * | 2010-12-28 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Wollastonite modified polypropylene composite material |
| CN104974418A (en) * | 2014-04-14 | 2015-10-14 | 中国石化扬子石油化工有限公司 | Polyropylene composite material and preparation method thereof |
| CN105504543A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | High-fluidity low-linearity-expansion-coefficient polypropylene composition and preparation method thereof |
| CN106543387A (en) * | 2015-09-16 | 2017-03-29 | 中国石化扬子石油化工有限公司 | A kind of high-performance eutectic refers to extrusion grade block polypropylene, its preparation method and the composition comprising it |
| CN108395627A (en) * | 2018-04-04 | 2018-08-14 | 大连环球矿产股份有限公司 | A kind of automobile-used polypropylene dedicated material and preparation method thereof |
| CN110951166A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | High-performance polypropylene material and preparation method thereof |
| CN112552613A (en) * | 2020-11-25 | 2021-03-26 | 金发科技股份有限公司 | High-toughness high-rigidity ABS composite material special for storage battery shell and preparation method and application thereof |
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| CN101020775A (en) * | 2007-03-15 | 2007-08-22 | 复旦大学 | High strength and high toughness modified poly-propylene material |
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| CN102532692A (en) * | 2010-12-28 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Wollastonite modified polypropylene composite material |
| CN102311583B (en) * | 2011-07-15 | 2013-07-10 | 上海俊尔新材料有限公司 | Rigidity-toughness balanced polypropylene |
| CN102311583A (en) * | 2011-07-15 | 2012-01-11 | 上海俊尔新材料有限公司 | Rigidity-toughness balanced polypropylene |
| CN102514330A (en) * | 2011-12-08 | 2012-06-27 | 上海普利特复合材料股份有限公司 | PVC cladded polypropylene micro-foamed plastic and its preparation technology |
| CN102532776A (en) * | 2011-12-21 | 2012-07-04 | 中国石油化工股份有限公司 | Low-smell rigid-tough high-performance polypropylene composite material and preparation method thereof |
| CN104974418A (en) * | 2014-04-14 | 2015-10-14 | 中国石化扬子石油化工有限公司 | Polyropylene composite material and preparation method thereof |
| CN106543387A (en) * | 2015-09-16 | 2017-03-29 | 中国石化扬子石油化工有限公司 | A kind of high-performance eutectic refers to extrusion grade block polypropylene, its preparation method and the composition comprising it |
| CN105504543A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | High-fluidity low-linearity-expansion-coefficient polypropylene composition and preparation method thereof |
| CN108395627A (en) * | 2018-04-04 | 2018-08-14 | 大连环球矿产股份有限公司 | A kind of automobile-used polypropylene dedicated material and preparation method thereof |
| CN110951166A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | High-performance polypropylene material and preparation method thereof |
| CN112552613A (en) * | 2020-11-25 | 2021-03-26 | 金发科技股份有限公司 | High-toughness high-rigidity ABS composite material special for storage battery shell and preparation method and application thereof |
| WO2022110662A1 (en) * | 2020-11-25 | 2022-06-02 | 金发科技股份有限公司 | High-toughness and high-rigidity abs composite material dedicated to storage battery casings, preparation method therefor and application thereof |
| CN113549271A (en) * | 2021-08-12 | 2021-10-26 | 上海金发科技发展有限公司 | Flame-retardant polypropylene composite material and preparation method and application thereof |
| CN113549271B (en) * | 2021-08-12 | 2023-01-24 | 上海金发科技发展有限公司 | Flame-retardant polypropylene composite material and preparation method and application thereof |
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Application publication date: 20100630 |