CN103030891A - Long glass fiber-reinforced polypropylene composite material and preparation method thereof - Google Patents
Long glass fiber-reinforced polypropylene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103030891A CN103030891A CN2013100093336A CN201310009333A CN103030891A CN 103030891 A CN103030891 A CN 103030891A CN 2013100093336 A CN2013100093336 A CN 2013100093336A CN 201310009333 A CN201310009333 A CN 201310009333A CN 103030891 A CN103030891 A CN 103030891A
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- long glass
- mixing
- reinforced polypropylene
- correcting agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 46
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 43
- -1 polypropylene Polymers 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 239000011521 glass Substances 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003365 glass fiber Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000005755 formation reaction Methods 0.000 claims description 7
- 230000002035 prolonged Effects 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000003078 antioxidant Effects 0.000 abstract description 6
- 239000003963 antioxidant agent Substances 0.000 abstract description 6
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract description 3
- 238000003490 calendering Methods 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound 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h0Pgo8L3N2Zz4K [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound 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C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound 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- 125000004805 propylene group Chemical group 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Classifications
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- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention discloses a long glass fiber-reinforced polypropylene composite material and an online mixing preparation method thereof. The long glass fiber-reinforced polypropylene composite material comprises the following components by weight: 50-65% of polypropylene, 20-35% of long glass fiber, 1-10% of compatilizer, 1-5% of toughener, 0.1-0.8% of antioxidant, 0.1-0.5% of crystal form modifying agent and 5-20% of filler. The online mixing preparation method comprises the following steps: uniformly mixing the polypropylene, various auxiliaries and the filler, then feeding a mixture into a first-order equidirectional twin-screw extruder and performing online mixing; then introducing into a second-order counter-rotating parallel twin-screw extruder, also introducing the glass fiber after surface treatment and preheating from the second-order extruder, mixing with the material, cutting, opening, homogenizing, building pressure, extruding, performing three-roller calendering, shaping, cutting and then packaging, wherein the beta crystal form modifying agent is adopted to improve the performances of the composite material, the mixing and the homogenization of the glass fiber during the shaping process are operated by different machines so as to be conductive to fully mixing the material, the speeds of the two extruders are respectively controlled, and the length of the glass fiber is controllable.
Description
Technical field
The invention belongs to the composites processing technology field, relate to a kind of long glass fiber-reinforced polypropylene materials and preparation method thereof, particularly a kind of crystal formation modification long glass fiber-reinforced polypropylene materials and online compounding preparation method thereof based on two rank twin-screw extrusion.
Background technology
Polypropylene is as the most general at present domestic and international thermoplastic polymer, in the plastics field, have very widely and use, it is the important channel of improving its over-all properties that polypropylene strengthens by glass, long glass fiber reinforced polypropylene composite material is developed rapidly in recent years, because it is high-strength light not only, also have the advantages such as good weathering resistance, good processibility, recoverable, in automotive light weight technology, environmental protection, bringing into play extremely important effect.In recent years, Long Glass Fiber Reinforced PP Composite was carried out many researchs both at home and abroad.In the past, about the main preparation method of glass fiber reinforced polypropylene composite material in-situ polymerization dipping technique, powder dipping technique and melt impregnation technology etc. were arranged.Patent of invention 200810020936.5 " long glass fiber reinforced polypropylene material and preparation method thereof " discloses a kind of employing melt impregnation technology, several section chief's glass fibre are incorporated into makes long glass fibres fully be flooded by melt in the molten bath, boundling coats again, die head exit discharging from broadening formation, cooling, pelletizing namely obtain the long glass fiber reinforced polypropylene pellet at last.Although this method has been strengthened the dipping effect of glass and resin, glass skewness or glass fiber bundling phenomenon very easily appear, even glass emergence on the surface, affect Mechanical Properties of Products.Patent of invention 201010602231.1 " a kind of long glass fiber reinforced polypropylene material and preparation method thereof " discloses a kind of employing melt impregnation technology, the melt polypropylene that long glass fibres is introduced with high fusion index fully floods, cooling, pelletizing obtain the long glass fiber reinforced polypropylene pellet at last.Although this method adopts the high fusion index polypropylene to strengthen the dipping effect of glass and resin, then effect is limited for acrylic resin that middle eutectic refers to, refers to that because height is molten the polypropylene molecule amount is little, and it is polyacrylic good to hang down during mechanical property is not so good as.
In sum, the preparation method for the preparation of long glass fiber-reinforced polypropylene materials all exists various shortcomings to some extent at present, and the cost performance of prepared matrix material is still undesirable.At present, there is two types processing technology of preparing in long glass fiber-reinforced polypropylene: a kind of is to be processed into first the long glass fiber-reinforced polypropylene pellet, and then the two step method technology of preparing of process injection or extrusion moulding; Another kind is the single stage method technology of preparing, i.e. compounding resin, additive, glass on production line, be directly formed to goods, save granulation middle-chain, the advantage of the online compounding moulding of long glass fiber-reinforced polypropylene single stage method mainly contains two: reduced the cooling of processing pellet, the heat-processed of reshaping, save the energy, compare traditional moulding and saved at least 20% energy consumption; Another is to avoid second-heating to cause the polypropylene Partial digestion, the goods excellent combination property.Because raising has also guaranteed the length of fiber in the goods, and the intensity of goods, rigidity are improved.Also have in addition shaping cycle short, goods do not have the corner refuse, reclaim the advantages such as convenient, abroad progressively apply.
Summary of the invention
For the deficiencies in the prior art, provide a kind of by changing the crystalling propylene type long glass fiber reinforced polypropylene composite material and based on the online compounding preparation method of single stage method of the Long Glass Fiber Reinforced PP Composite of two rank twin-screw extrusion.
The online compounding equipment of one step processing of the Long Glass Fiber Reinforced PP Composite based on two rank twin-screw extrusion of the present invention comprises following a few part: the first rank parallel dual-screw extruding machine, second-order counter rotation twin screw extruder, glass surface treating machine, hanger-style die, tri-roll press machine, typing forming machine and cutting machine.The first rank parallel dual-screw extruding machine is equally divided into 6~8 temperature control districts, and screw diameter is 20~80mm, and length-to-diameter ratio L/D is 32~52; The second-order counter rotation twin screw extruder is equally divided into 5~7 temperature control districts, screw diameter is 28~75mm, L/D is 8~18, two extruders can be distinguished speed governing, temperature adjustment, pressure regulation, screw element adopts the cord wood combination, make that polypropylene mixes, homogenizing is more abundant, make glass in matrix, keep desirable length, homogeneity and cohesiveness; The glass roving is introduced the second-order counter rotation twin screw extruder with 100~125 ℃ of steady temperatures by bundle pipes; Hanger-style die pressure is 5~25MPa.
Consider consistency in the co-mixing system moulding process, rheological etc., choose reasonable the content of each component in the prescription of each component and the control co-mixing system in the compound system, through lot of experiments, the present invention proposes a kind of polynary compound system, and adopt a kind of nucleator that can change the crystalling propylene type, make the processability of long glass fiber-reinforced polypropylene materials good, thereby improved the over-all properties of matrix material.
Component and the weight percent of preparation long glass fiber reinforced polypropylene composite material prescription of the present invention are as follows:
Wherein, described long glass fibres is the special-purpose continuously roving of long glass fiber-reinforced polypropylene, mainly as strongthener, plays the skeleton supporting role;
Wherein, described compatilizer is one or both mixing of maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene, and maleic anhydride grafting ratio is greater than 1;
Wherein, described toughner is one or more mixing of polyolefin elastomer, styrene block copolymer, double-peak high-density polytene;
Wherein, described oxidation inhibitor is one or both mixing of antioxidant 1010, irgasfos 168;
Wherein, described crystal formation properties-correcting agent is one or more mixing of beta crystal properties-correcting agent GX-5, beta crystal properties-correcting agent WBG, beta crystal properties-correcting agent NT-C;
Wherein, described filler is one or both mixing in superfine talcum powder, the calcium carbonate superfine powder.The filler specification is all greater than 2000.
Prepare above-mentioned long glass fiber reinforced polypropylene composite material method, may further comprise the steps:
Polypropylene, compatilizer, toughner, oxidation inhibitor, crystal formation properties-correcting agent and filler are mixed, feed the first rank twin screw extruder, processing temperature is at 170~240 ℃; Then inject the second-order twin screw extruder, introduced simultaneously the in advance long glass fibres of dissipation of heat, processing temperature is at 180~240 ℃; Material is extruded from hanger-style die, packs after three roll-ins are prolonged, finalize the design, cut, dispatches from the factory.
Through evidence, adopt the online compounding preparation method of long glass fiber-reinforced polypropylene sheet material, the fiber glass reinforced polypropylene composite sheet that obtains, glass and bond matrix are respond well, the sheet material excellent combination property.
Description of drawings
Fig. 1 is the X-ray diffractogram of matrix material when not adding beta nucleater.
Fig. 2 is the X-ray diffractogram of matrix material when adding 0.2% beta nucleater.
Embodiment
Now to have adopted two rank twin screw extruder arranged vertically, the first rank parallel dual-screw extruding machine screw diameter is 60mm, and L/D is 40, and rotating speed is 85RPM, be equally divided into 7 temperature control districts, screw rod district service temperature is 165 ℃, 178 ℃, and 180 ℃, 185 ℃, 190 ℃, 190 ℃, 190 ℃.Second-order anisotropic parallel twin-screw extruding machine, screw diameter are 70mm, and L/D is 9, and rotating speed is 45RPM, are divided into 5 temperature control districts, and service temperature is 190 ℃, 195 ℃, and 195 ℃, 190 ℃, 190 ℃.190 ℃ of die head temperatures, die pressure 10MPa are example.
Embodiment 1
Homo-polypropylene with 56.5%, 4% maleic anhydride inoculated polypropylene, 4% polyolefin elastomer, 0.1% antioxidant 1010,0.2% irgasfos 168,0.2% beta crystal properties-correcting agent WBG and 5% talcum powder mix and add the First forcing machine, simultaneously the glass fibre of 30% preheating is introduced second forcing machine, after three roll-ins are prolonged, finalize the designs, cut, pack, dispatch from the factory.
Embodiment 2
Homo-polypropylene with 56.7%, 4% maleic anhydride inoculated polypropylene, 4% polyolefin elastomer, 0.1% antioxidant 1010,0.2% irgasfos 168,5% talcum powder mix adding First forcing machine, simultaneously the glass fibre of 30% preheating is introduced second forcing machine, after three roll-ins are prolonged, finalize the designs, cut, pack, dispatch from the factory.
Embodiment 3
Co-polypropylene with 56.5%, 4% maleic anhydride grafted polyethylene, 4% styrene block copolymer, 0.2% antioxidant 1010,0.1% irgasfos 168,0.2% beta crystal properties-correcting agent NT-C and 5% calcium carbonate mix and add the First forcing machine, simultaneously the glass fibre of 30% preheating is introduced second forcing machine, after three roll-ins are prolonged, finalize the designs, cut, pack, dispatch from the factory.
Embodiment 4
Co-polypropylene with 56.7%, 4% maleic anhydride grafted polyethylene, 4% styrene block copolymer, 0.2% antioxidant 1010,0.1% irgasfos 168,5% calcium carbonate mix adding First forcing machine, simultaneously the glass fibre of 30% preheating is introduced second forcing machine, after three roll-ins are prolonged, finalize the designs, cut, pack, dispatch from the factory.
Add rear polyacrylic Crystal type by accompanying drawing 1 and the visible beta crystal properties-correcting agent of accompanying drawing 2 wide-angle x-ray diffracting spectrums change has occured, embodiment gained glass fiber content, glass mean length, tensile strength, flexural strength, shock strength have been tested respectively, the result can draw the long glass fiber reinforced polypropylene composite material excellent combination property that this online compounding preparation method and beta crystal modifier modification crystalling propylene crystal formation obtain as described in the following table.
The material properties test result is as follows:
Content measurement | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
Glass fiber content | % | 30 | 30 | 30 | 30 |
The glass mean length | mm | 12.4 | 12.2 | 12.0 | 12.1 |
Tensile strength | MPa | 89.32 | 86.45 | 83.06 | 76.27 |
Flexural strength | MPa | 179.47 | 167.21 | 146.42 | 136.52 |
Shock strength | KJ/m 2 | 48.01 | 40.21 | 53.35 | 43.95 |
Heat-drawn wire | ℃ | 168 | 168 | 168 | 168 |
Claims (3)
1. long glass fiber reinforced polypropylene composite material is characterized in that being prepared from by following substances is compound according to the mass percent meter:
2. long glass fiber reinforced polypropylene composite material according to claim 1 is characterized in that, described crystal formation properties-correcting agent is one or more mixing of beta crystal properties-correcting agent GX-5, beta crystal properties-correcting agent WBG, beta crystal properties-correcting agent NT-C.
3. method for preparing long glass fiber reinforced polypropylene composite material claimed in claim 1 based on the online compounding equipment of two rank twin-screw extrusion may further comprise the steps:
Polypropylene, compatilizer, toughner, oxidation inhibitor, crystal formation properties-correcting agent and filler are mixed, feed the first rank twin screw extruder, processing temperature is at 170~240 ℃; Then inject the second-order twin screw extruder, introduced simultaneously the in advance long glass fibres of dissipation of heat, processing temperature is at 180~240 ℃; Material is extruded from hanger-style die, packs after three roll-ins are prolonged, finalize the design, cut, dispatches from the factory.
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CN103937093A (en) * | 2014-03-21 | 2014-07-23 | 浙江俊尔新材料股份有限公司 | Long glass fiber reinforced polypropylene composite material and preparation method |
CN103937094A (en) * | 2014-04-02 | 2014-07-23 | 广东天保新材料有限责任公司 | Screwing burst resisting enhanced polypropylene material as well as preparation method and application thereof |
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CN103937093A (en) * | 2014-03-21 | 2014-07-23 | 浙江俊尔新材料股份有限公司 | Long glass fiber reinforced polypropylene composite material and preparation method |
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CN104479216A (en) * | 2014-11-20 | 2015-04-01 | 苏州新区佳合塑胶有限公司 | Automobile diversion plate material |
CN104497418A (en) * | 2014-12-18 | 2015-04-08 | 安徽科聚新材料有限公司 | Polypropylene composite material for spinning tube and preparation method of polypropylene composite material |
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CN112063092B (en) * | 2020-09-18 | 2021-09-14 | 湖南大学 | High-toughness long glass fiber reinforced random copolymerization polypropylene composite material and preparation method thereof |
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