CN110452452A - A kind of high performance composite long fiber reinforced polypropylene material and preparation method thereof - Google Patents

A kind of high performance composite long fiber reinforced polypropylene material and preparation method thereof Download PDF

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CN110452452A
CN110452452A CN201910748034.1A CN201910748034A CN110452452A CN 110452452 A CN110452452 A CN 110452452A CN 201910748034 A CN201910748034 A CN 201910748034A CN 110452452 A CN110452452 A CN 110452452A
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fiber
reinforced polypropylene
fiber reinforced
high performance
long fiber
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徐凯华
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Shanghai Huahe Composite Material Co Ltd
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Shanghai Huahe Composite Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

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Abstract

The present invention relates to a kind of high performance composite long fiber reinforced polypropylene materials and preparation method thereof, it is specifically made of the raw material of following parts by weight: 30~70 parts of acrylic resin, 10~20 parts of continuous glass fibre, 10-20 parts of continuous basalt fiber, 2~10 parts of efficient compatilizer；Present invention has an advantage that introducing the second fibre reinforcement of high-performance, the novel basalt fiber of resistant to shearing as compounding, and use the long fibre processing work mode of " melt impregnation, particle length cuts ", reinforced polypropylene material middle fiber after processing and forming is remained to the maximum extent is effectively retained length.Compared with the reservation length of 1.5-2mm in conventional long glass fiber-reinforced polypropylene materials, the material of this compound long fiber reinforced retains length with considerably higher fiber after processing and forming, reach as high as 2.5-4mm, and fiber dispersion is more uniform, the main inflexible target such as tensile strength, impact strength of material improves 30-50% on year-on-year basis, wherein tensile strength is up to 140MPa or more, impact strength up to 70kJ/m2More than.

Description

A kind of high performance composite long fiber reinforced polypropylene material and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of high performance compound long glass fiber-reinforced polypropylene Material and preparation method thereof.
Background technique
Polypropylene (PP) is a kind of crystalline polyolefin material being made of the hydrocarbon molecules chain being saturated, hydrocarbon point of saturation Subchain and crystallinity impart the good chemical resistance of the material and relatively good mechanical property, can be used as high performance thermoplastic One of the ideal selection of property based composites.The maximum advantage of PP material is that synthesis technology is simple, and polymerized monomer can be from refining Therefore the by-product of oily industry compares other thermoplastic matrix materials such as ABS, PC, PA, PBT etc., PP has clearly Inexpensive, high production advantage.
With the continuous upgrading of the fields products such as modern automobile, industrial electronic, household electrical appliance, for low cost, The mechanics such as rigidity, intensity and the impact resistance of the performance requirement that high performance thermoplastic composite proposes, especially material The requirement of performance indicator is increasingly harsh, and performance brought by traditional method of modifying such as talc, short fine enhancing increases Relatively limited, in recent years, a kind of long glass fiber reinforced (LFT) processing method of " online melt impregnation, particle length are cut " has become One of study on the modification hot spot of reinforced polypropylene material, since fiber reservation length is high, neat and orderly in its pelletizing particle, Therefore, there is clearly improvement for the mechanical property of polypropylene matrix material.
However, the research of long glass fiber-reinforced polypropylene (LFT-PP) material in recent years is mostly focused on material multifunction Improvement, if CN108485056, CN108250566, CN107964167 focus on the LFT-PP investigation of materials of anti-flammability, lead to It crosses the Halogen of additional different size or has the mode of halogen fire retardant system to realize that the flame retardant property of material is promoted； It is special that CN107254104, CN106750950 are then that the low smell for focusing on LFT-PP material, low organic matter distribute the environmental protection such as (VOC) The improvement of property.From the foregoing, it will be observed that be actually to have fallen into certain mechanical property bottleneck period for current LFT-PP investigation of materials, Its basic reason is the performance limitation of PP matrix, glass fibre (GF) reinforcement, especially glass fibre GF, rigidity, Other reinforcements such as metallic fiber, carbon fiber, whisker etc. will be much lower on year-on-year basis for modulus.For this performance deficiency problem, when Preceding existing settling mode is third type high-performance matrix or the reinforcement being added other than PP, GF, such as A kind of compound long glass fiber-reinforced polypropylene materials of nano material described in CN105623097A, the nanometer of 1-5% enhance female Grain can obviously improve the mechanical performance index of LFT-PP material, but the improvement degree of this performance also relies on point of nano material Bulk condition, therefore, it is necessary to be processed into the mode of master batch to be added, disperse, increase material processing process flow and at This；CN103709512A is the introduction of high performance nylon (PA) material then as the second resin matrix of LFT-PP, but by Different material characteristics between PP, PA, the alternate compatibility of the two is simultaneously bad, therefore, for the LFT-PP mechanics of materials The promotion amplitude of energy is actually very limited.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of high performance composite long fiber enhancings poly- third Alkene material, for the relatively low inherent shortcomings of mechanical properties such as polypropylene rigidity, the intensity for being saturated hydrocarbon molecules chain structure, Yi Jidan Situations such as one long glass fiber reinforced effect is limited, easy shear fracture is come by the way that second auxiliary reinforcement-basalt fibre is added The fiber compounding for realizing polypropylene enhancing system, coordinates to promote the reinforcing effect to PP matrix；In addition, passing through preferred specific standard And the efficient compatilizer of dosage, good interphase interface compatibility is realized, this is strong to the stretching for improving PP composite material Degree and impact strength are even more important.
The purpose of the present invention is achieved through the following technical solutions:
A kind of high performance composite long fiber reinforced polypropylene material, the raw material including following parts by weight:
Further, the acrylic resin is homopolymerization or co-polypropylene, in 230 DEG C, the test condition of 2.16kg Under, melt index 15-90g/10min.
Further, the continuous glass fibre is direct roving, filament diameter 17um, typical line density For 1200-2400tex.
Further, the continuous basalt fiber is direct roving, and filament diameter 10-13um is typical Line density is 600-1200tex.
Further, the efficient compatilizer is that maleic anhydride inoculated polypropylene PP-MAH, Glycidyl methacrylate are sweet The one of grease graft polypropylene PP-GMA, glycidyl methacrylate graft ethylene-ethyl acetate copolymer EVA-GMA etc. Kind is several.
The second object of the present invention is to provide this high performance composite long fiber reinforced polypropylene material, including following Step:
(1) acrylic resin, efficient compatilizer are weighed by the parts by weight, are uniformly mixed, obtain mixed raw material:
(2) mixed raw material after drying is placed in the main feeding for the double screw extruder that one tightly engages rotating Vortex It in storehouse, is added in the machine barrel of extruder through feed screw, extruder screw diameter is 36mm, and draw ratio L/D is 44, main barrel Each zone temperature setting exported from feed opening to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
(3) continuous glass fibre, continuous basalt fiber are respectively placed on creel, are carried out through jockey pulley pre-tension Dividing sinker, by parallel arrangement after different spool export, then enter in immersion-type chamber with acrylic resin melt it is mutually compound, soak Profit cools down rear haulage by impregnation die export, through sink to pelleter, is chopped as the long fibre enhanced polypropylene of 10-15mm length Alkene pellet.
Compared with prior art, the invention has the following beneficial effects:
1, firstly, the PP matrix selected by ensuring possesses good processing fluidity (MFR >=30g/10min) Under the premise of, it is preferably formed with polymerization catalyzed by metallocene, the acrylic resin trade mark with high-crystallinity, high stereoregular characteristic, Ensure selected PP Resin crystallization degree Xc by same, same ordered structure strand ratio complete in raising acrylic resin >=90%, PP matrix resin tensile strength, in 1800MPa or more, are subsequent variety classes fiber in 38MPa or more, bending modulus Compounding enhancing benefit good resin matrix is provided.
2, more it is essential that mostly using Single Fiber to increase greatly for traditional long glass fiber-reinforced polypropylene (LFT-PP) research Qiang Ti, and only focus on unlike the mechanical performance index under normal condition (standard injection molding batten), it is introduced in the present invention The high rigidity of certain proportion (5-25 parts), high-modulus, resistant to shearing abrasion basalt fibre, as traditional fiberglass reinforced body Effective compound ligand.Since the mechanical performance index of basalt fibre itself will be substantially better than conventional glass fibre, fiber surface Activation energy is high, polarity is stronger, it is easier to form good interfacial bond with matrix resin and compatilizer.3, it provides according to the present invention The resulting composite long fiber reinforced polypropylene material of technical solution, not only the rigidity under normal condition and impact resistance have centainly The promotion of degree, and particular, it is important that when simulating product injection molding and cutting out sample test, the material of this composite long fiber enhancing There are considerably higher tensile strength and impact strength, conventional long glass fiber reinforced system, above-mentioned intensity index mention on year-on-year basis Increasing degree degree is all 30% or more, and tensile strength reaches as high as 140MPa or more, and impact strength is in 70kJ/m2More than, very Close to the mechanical performance index of short glass fiber reinforced nylon 6 material；And it further can by comparing fiber reservation length therein To know, after the reinforcement of this compound roving glass fiber ties up to simulation injection molding, fiber retains length up to 2.5-4mm in product, and routinely Long glass fiber reinforced system only have 1.5-2mm, it is evident that it is entire fine since the basalt fibre more resistant to abrasion, resistant to shearing is added It is reduced significantly when dimension reinforcement ties up to injection molding with the shear fracture phenomenon between screw rod barrel and threaded block, fiber retains length It is obviously improved, such characteristic is complicated for some mould structures in automobile and industrial electronic, shearing mixing degree is strong Support rack type product injection molding have fabulous application value, can obviously improve gained product integral rigidity and intensity.
Specific embodiment
Below by specific embodiment, the present invention is described further, and the embodiment is merely to illustrate this hair It is bright rather than limiting the invention.
The embodiment of the present invention is raw materials used:
PP-1:Y2600T, oil of SPC, 230 DEG C, MFR is 30 under the conditions of 2.16kg, crystallinity Xc 73%.
PP-2:HJ8030, northern Hua Jin Chemical Co., Ltd., 230 DEG C, MFR is 32 under the conditions of 2.16kg, crystallinity Xc is 92%
PP-3:HX3900, SK Chemical, South Korea, 230 DEG C, MFR is 32 under the conditions of 2.16kg, crystallinity Xc 95%.
Continuous glass fibre: GF-988A-2000, fibre diameter 17um, megalith glass, typical line density are 2000tex.
Continuous basalt fiber: BR13-800, fibre diameter 13um, the limited public affairs of Jiangsu sky dragon continuous basalt fiber share Department, typical line density are 800tex.
Efficient compatilizer -1: maleic anhydride inoculated polypropylene PP-MAH, Jiangsu Jia Yirong compatilizer Co., Ltd, chemistry drop Determining method test grafting rate is 1.0%.
Efficient compatilizer -2: glycidyl methacrylate graft Ethylene-vinyl acetate EVA-GMA, self-control, chemistry drop Determining method test grafting rate is 0.75%, by double screw extruder, causes GMA/ styrene St mixing by peroxide initiator Object is grafted molten state EVA copolymer and obtains.
Properties of product test:
Tensile property: it by the batten size of ISO527-2 defined, is tested after being molded standard batten, test rate is 5mm/min is tested under room temperature (23 DEG C).
Bending property: by the batten size of IS178 defined, being tested after being molded standard batten, and test span is 64mm, test rate 2mm/min are tested under room temperature (23 DEG C).
Impact property: it by the batten size of ISO179-1 prescribed by standard, is tested after being molded standard batten, in freely-supported It carries out on beam shock machine, batten non-notch, is tested under room temperature (23 DEG C).
Product cuts out sample test: shot size is the template of 355 × 100 × 3.2mm, on computer-controlled accurate sanction model machine Standard-sized tensile strength, impact strength test specimens are intercepted by PARALLEL FLOW direction (∥) and perpendicular flow direction (⊥) respectively Item places the test for carrying out tensile strength, impact strength after 48h in 23 DEG C, the standard environment of 50%RH, obtains product and cut out sample Performance data.
Fiber retains length testing: intercepting fritter sample from product and is placed within crucible, in 650 DEG C in Muffle furnace Lower calcination 2h, burning residue are dissolved with ethanol solution, are then observed under Lycra DMi8 inverted metallurgic microscope, and be combined Leica LAS Image Analysis image analysis software obtains the distribution curve that fiber retains length, is calculated according to curve Distribution of lengths interval censored data corresponding to 90% fiber.
Embodiment 1
Acrylic resin, efficient compatilizer are weighed by 1 data of embodiment shown in table 1, is uniformly mixed, it is former to obtain mixing Material:
Mixed raw material after drying is placed in the main feeding bin for the double screw extruder that one tightly engages rotating Vortex In, be added in the machine barrel of extruder through feed screw, extruder screw diameter be 36mm, draw ratio L/D be 44, main barrel from Each zone temperature setting that feed opening is exported to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, Engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
Continuous glass fibre, continuous basalt fiber are respectively placed on creel, divided through jockey pulley pre-tension Yarn, by parallel arrangement after different spool export, then enter in immersion-type chamber with acrylic resin melt it is mutually compound, infiltrate, Rear haulage is cooled down by impregnation die export, through sink to pelleter, is chopped as the long fibre enhanced polypropylene grain of 10-15mm length Material.
The formula table (unit: gram) of the high performance compound long glass fiber-reinforced polypropylene materials of table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
PP-1 70 -
PP-2 70 -
PP-3 68 63 60 65 -
Continuous glass fibre 15 15 15 15 20 30 -
Continuous basalt fiber 10 10 15 15 10 -
Efficient compatilizer -1 5 2 5 -
Efficient compatilizer -2 5 7 10 -
Embodiment 2
Acrylic resin, efficient compatilizer are weighed by 2 data of embodiment shown in table 1, is uniformly mixed, it is former to obtain mixing Material:
Mixed raw material after drying is placed in the main feeding bin for the double screw extruder that one tightly engages rotating Vortex In, be added in the machine barrel of extruder through feed screw, extruder screw diameter be 36mm, draw ratio L/D be 44, main barrel from Each zone temperature setting that feed opening is exported to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, Engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
Continuous glass fibre, continuous basalt fiber are respectively placed on creel, divided through jockey pulley pre-tension Yarn, by parallel arrangement after different spool export, then enter in immersion-type chamber with acrylic resin melt it is mutually compound, infiltrate, Rear haulage is cooled down by impregnation die export, through sink to pelleter, is chopped as the long fibre enhanced polypropylene grain of 10-15mm length Material.
Embodiment 3
Acrylic resin, efficient compatilizer are weighed by 3 data of embodiment shown in table 1, is uniformly mixed, it is former to obtain mixing Material:
Mixed raw material after drying is placed in the main feeding bin for the double screw extruder that one tightly engages rotating Vortex In, be added in the machine barrel of extruder through feed screw, extruder screw diameter be 36mm, draw ratio L/D be 44, main barrel from Each zone temperature setting that feed opening is exported to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, Engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
Continuous glass fibre, continuous basalt fiber are respectively placed on creel, divided through jockey pulley pre-tension Yarn, by parallel arrangement after different spool export, then enter in immersion-type chamber with acrylic resin melt it is mutually compound, infiltrate, Rear haulage is cooled down by impregnation die export, through sink to pelleter, is chopped as the long fibre enhanced polypropylene grain of 10-15mm length Material.
Embodiment 4
Acrylic resin, efficient compatilizer are weighed by 4 data of embodiment shown in table 1, is uniformly mixed, it is former to obtain mixing Material:
Mixed raw material after drying is placed in the main feeding bin for the double screw extruder that one tightly engages rotating Vortex In, be added in the machine barrel of extruder through feed screw, extruder screw diameter be 36mm, draw ratio L/D be 44, main barrel from Each zone temperature setting that feed opening is exported to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, Engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
Continuous glass fibre, continuous basalt fiber are respectively placed on creel, divided through jockey pulley pre-tension Yarn, by parallel arrangement after different spool export, then enter in immersion-type chamber with acrylic resin melt it is mutually compound, infiltrate, Rear haulage is cooled down by impregnation die export, through sink to pelleter, is chopped as the long fibre enhanced polypropylene grain of 10-15mm length Material.
Embodiment 5
Acrylic resin, efficient compatilizer are weighed by 5 data of embodiment shown in table 1, is uniformly mixed, it is former to obtain mixing Material:
Mixed raw material after drying is placed in the main feeding bin for the double screw extruder that one tightly engages rotating Vortex In, be added in the machine barrel of extruder through feed screw, extruder screw diameter be 36mm, draw ratio L/D be 44, main barrel from Each zone temperature setting that feed opening is exported to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, Engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
Continuous glass fibre, continuous basalt fiber are respectively placed on creel, divided through jockey pulley pre-tension Yarn, by parallel arrangement after different spool export, then enter in immersion-type chamber with acrylic resin melt it is mutually compound, infiltrate, Rear haulage is cooled down by impregnation die export, through sink to pelleter, is chopped as the long fibre enhanced polypropylene grain of 10-15mm length Material.
Comparative example 1
Acrylic resin, efficient compatilizer are weighed by 1 data of comparative example shown in table 1, is uniformly mixed, it is former to obtain mixing Material:
Mixed raw material after drying is placed in the main feeding bin for the double screw extruder that one tightly engages rotating Vortex In, be added in the machine barrel of extruder through feed screw, extruder screw diameter be 36mm, draw ratio L/D be 44, main barrel from Each zone temperature setting that feed opening is exported to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, Engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
Continuous glass fibre is placed on creel, dividing sinker is carried out through jockey pulley pre-tension, is led by different spools Out after parallel arrangement, then enter immersion-type chamber in acrylic resin melt it is mutually compound, infiltration, by impregnation die export, pass through The cooling rear haulage of sink is chopped to pelleter as the long glass fiber-reinforced polypropylene pellet of 10-15mm length.
Comparative example 2
25% short glass fiber reinforced nylon 6 composite material, B3EG5, BASF Aktiengesellschaft are commercially available.
The test result of the high performance compound long glass fiber-reinforced polypropylene materials of table 2
The testing of materials data of each embodiment and comparative example from table 2 are it is found that for fiber-reinforced polymer-matrix composite wood For material, performance three elements are that " matrix, interface, reinforcement " has direct influence to the mechanical property of material.By reality Apply the data of example 1~3 and comparative example 1 it is found that the basalt fibre as the second reinforcement to can obviously improve long glass fiber reinforced poly- The rigidity and shock resistance of propylene material, especially tensile strength, either injection molding batten or product cut out sample, promote width It spends all in 10-15%, and by advanced optimizing PP resin matrix and interfacial compatibilizer, this composite long fiber reinforced polypropylene Mechanical property performance can also obtain further tremendous increase, in embodiment 4, as glass/basalt fibre=1:1, The tensile strength of material standard batten reaches peak 143MPa, and the tensile strength that product cuts out sample is 108MPa, year-on-year routine Glass system (comparative example 1) promotes amplitude 30% or more, and the impact strength of batten and sanction sample is also respectively from 56kJ/m2、 49kJ/m2It is promoted to 73kJ/m2、63kJ/m2.On the one hand it is strong due to basalt fibre itself that above-mentioned mechanical property, which improves, Degree and rigidity are just better than glass fibre, and on the other hand, since the endurance of cutting of basalt fibre is more preferable, fiber is after melting mixing Crack conditions are kept preferably, and the reservation length of 90% fiber is significantly promoted to 2.5-4.0mm from 1.5-2.0mm, this is to cut out Sample performance obtains the basic reason being obviously improved.And comparative example 4 and comparative example 2 are it is found that this be based on " matrix, interface, increasing The main performance index such as (tensile strength, impact strength) of the composite long fiber reinforced polypropylene material of strong body " three elements optimization Typical engineering plastics (glass fiber reinforced nylon 6 material) data have been in close proximity to, and material cost only has the 60- of the latter 70% or so, good material cost performance is embodied, and processing temperature and energy consumption are lower, has had and good economical and environmentally friendly imitate Benefit.
A kind of composite long fiber reinforced polypropylene material and preparation method thereof that the present invention is described, from the three of composite material Element, i.e. " matrix, glass, interface " three aspect are started with jointly, with being used in compounding for variety classes fibre reinforcement, are aided with efficiently The polypropylene matrix resin of compatilizer and high rigidity, so that it is poly- to obtain the more traditional long glass fiber reinforced of rigidity, intensity, impact resistance The more excellent reinforced polypropylene material of propylene, especially cutting out sample prescription face in simulation product is even more to have obviously to improve effect Fruit, this being answered to promoting structural product (bracket, frame, the shell etc.) of the material in some fields such as automobile, electronic apparatus With, accelerate above-mentioned field " mould Dai Gang " material category to substitute process to be obviously performance advantage.

Claims (6)

1. a kind of high performance composite long fiber reinforced polypropylene material, it is characterised in that: the raw material including following parts by weight:
2. a kind of high performance composite long fiber reinforced polypropylene material according to claim 1, it is characterised in that: described Acrylic resin be homopolymerization or co-polypropylene, under 230 DEG C, the test condition of 2.16kg, melt index 15-90g/ 10min。
3. a kind of high performance composite long fiber reinforced polypropylene material according to claim 1, it is characterised in that: described Continuous glass fibre be direct roving, filament diameter 17um, typical line density be 1200-2400tex.
4. a kind of high performance composite long fiber reinforced polypropylene material according to claim 1, it is characterised in that: described Continuous basalt fiber be direct roving, filament diameter 10-13um, typical line density be 600-1200tex.
5. a kind of high performance composite long fiber reinforced polypropylene material according to claim 1, it is characterised in that: described Efficient compatilizer be maleic anhydride inoculated polypropylene PP-MAH, glycidyl methacrylate graft polypropylene PP-GMA, One or more of glycidyl methacrylate graft ethylene-ethyl acetate copolymer EVA-GMA.
6. the preparation method of high performance composite long fiber reinforced polypropylene material described in claim 1-5 is one of any, special Sign is, comprising the following steps:
(1) acrylic resin, efficient compatilizer are weighed by the parts by weight, are uniformly mixed, obtain mixed raw material:
(2) mixed raw material after drying is placed in the main feeding bin for the double screw extruder that one tightly engages rotating Vortex In, be added in the machine barrel of extruder through feed screw, extruder screw diameter be 36mm, draw ratio L/D be 44, main barrel from Each zone temperature setting that feed opening is exported to head are as follows: 100 DEG C, 190 DEG C, 200 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, Engine speed is 300 revs/min, and gained molten state acrylic resin is injected into immersion-type chamber through extruding dies.
(3) continuous glass fibre, continuous basalt fiber are respectively placed on creel, are divided through jockey pulley pre-tension Yarn, by parallel arrangement after different spool export, then enter in immersion-type chamber with acrylic resin melt it is mutually compound, infiltrate, Rear haulage is cooled down by impregnation die export, through sink to pelleter, is chopped as the long fibre enhanced polypropylene grain of 10-15mm length Material.
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CN111040299A (en) * 2019-12-26 2020-04-21 衡水瑞纤新材料科技有限公司 High-impact high-toughness composite material and preparation method thereof
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Application publication date: 20191115