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 PDF

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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
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CN
China
Prior art keywords
glass fiber
long glass
mixing
reinforced polypropylene
correcting agent
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CN2013100093336A
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Chinese (zh)
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董擎之
张彦庆
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East China University of Science and Technology
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East China University of Science and Technology
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Priority to CN2013100093336A priority Critical patent/CN103030891A/en
Publication of CN103030891A publication Critical patent/CN103030891A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/80Component parts, details or accessories; Auxiliary operations
    • B29B7/88Adding charges, i.e. additives
    • B29B7/90Fillers or reinforcements, e.g. fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58Component parts, details or accessories; Auxiliary operations
    • B29B7/72Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • B29B9/14Making granules characterised by structure or composition fibre-reinforced
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means 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
    • B29C48/40Means 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel 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

A kind of long glass fiber reinforced polypropylene composite material and preparation method thereof
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.
CN2013100093336A 2013-01-09 2013-01-09 Long glass fiber-reinforced polypropylene composite material and preparation method thereof Pending CN103030891A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104059293A (en) * 2014-06-25 2014-09-24 福建海源新材料科技有限公司 LFT-D (Long-Fiber Reinforce Thermoplastic Direct) forming method of building template filled with calcium carbonate
CN104076134A (en) * 2014-06-24 2014-10-01 巨石集团有限公司 Method for testing shear dispersion performance of glass fibers in thermoplastic plastics
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
CN106554561A (en) * 2015-09-28 2017-04-05 常熟江南玻璃纤维有限公司 A kind of new composite of mechanical property flexible variable and preparation method thereof
CN110284258A (en) * 2019-07-04 2019-09-27 芜湖莫森泰克汽车科技股份有限公司 A kind of integrated car glass-frame riser guide rail making material and preparation method thereof
CN112063092A (en) * 2020-09-18 2020-12-11 湖南大学 High-toughness long glass fiber reinforced random copolymerization polypropylene composite material and preparation method thereof

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CN101381492A (en) * 2007-09-06 2009-03-11 比亚迪股份有限公司 Polypropylene composite material and preparation method thereof
CN102311585A (en) * 2011-09-13 2012-01-11 无锡利保科技发展有限公司 Long glass fiber reinforced polypropylene composite material and preparation method thereof
CN102617929A (en) * 2012-03-19 2012-08-01 深圳市科聚新材料有限公司 High-gloss modified polypropylene resin and preparation method for same

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Publication number Priority date Publication date Assignee Title
CN101381492A (en) * 2007-09-06 2009-03-11 比亚迪股份有限公司 Polypropylene composite material and preparation method thereof
CN102311585A (en) * 2011-09-13 2012-01-11 无锡利保科技发展有限公司 Long glass fiber reinforced polypropylene composite material and preparation method thereof
CN102617929A (en) * 2012-03-19 2012-08-01 深圳市科聚新材料有限公司 High-gloss modified polypropylene resin and preparation method for same

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103937093B (en) * 2014-03-21 2016-06-15 中广核俊尔新材料有限公司 A kind of long glass fiber reinforced polypropylene composite material and preparation method thereof
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
CN104076134A (en) * 2014-06-24 2014-10-01 巨石集团有限公司 Method for testing shear dispersion performance of glass fibers in thermoplastic plastics
CN104059293A (en) * 2014-06-25 2014-09-24 福建海源新材料科技有限公司 LFT-D (Long-Fiber Reinforce Thermoplastic Direct) forming method of building template filled with calcium carbonate
CN104059293B (en) * 2014-06-25 2016-08-17 福建海源新材料科技有限公司 A kind of LFT-D moulding process of calcium carbonate-filled building template
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
CN106554561A (en) * 2015-09-28 2017-04-05 常熟江南玻璃纤维有限公司 A kind of new composite of mechanical property flexible variable and preparation method thereof
CN110284258A (en) * 2019-07-04 2019-09-27 芜湖莫森泰克汽车科技股份有限公司 A kind of integrated car glass-frame riser guide rail making material and preparation method thereof
CN110284258B (en) * 2019-07-04 2020-08-28 芜湖莫森泰克汽车科技股份有限公司 Integrated automobile glass lifter guide rail manufacturing material and preparation method and application thereof
CN112063092A (en) * 2020-09-18 2020-12-11 湖南大学 High-toughness long glass fiber reinforced random copolymerization polypropylene composite material and preparation method thereof
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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