CN103937093B - A kind of long glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents

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

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CN103937093B
CN103937093B CN201410108339.3A CN201410108339A CN103937093B CN 103937093 B CN103937093 B CN 103937093B CN 201410108339 A CN201410108339 A CN 201410108339A CN 103937093 B CN103937093 B CN 103937093B
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long glass
fiber reinforced
glass fiber
composite material
reinforced polypropylene
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CN103937093A (en
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陈光剑
宋玉兴
陈永波
黄志杰
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Cgn Juner New Materials Co ltd
Cgn Juner Shanghai New Materials Co ltd
Zhongguang Nuclear Juner Zhejiang New Materials Co ltd
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Shanghai Jun'er New Material Co Ltd
Cgn Juner New Materials Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • 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
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • 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
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • 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
    • 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
    • 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
    • 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
    • B29C2948/92609—Dimensions
    • B29C2948/92638—Length
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention discloses a kind of long glass fiber reinforced polypropylene composite material with higher heat distortion temperature, it is made up of the raw material of following weight portion: polypropylene 100 parts, long glass fibres 30～70 parts, compatilizer 3～10 parts, mineral filler 3～12 parts, coupling agent 1～10 part, carborundum 1～5 part, beta crystal-type nucleater 1～5 part, magnesium salt whisker 1～5 part and processing aid 0～10 part, this material has higher heat distortion temperature, can use and have stability and property retention in broader temperature range. The preparation method that the invention also discloses a kind of long glass fiber reinforced polypropylene composite material, adopts existing double screw extruder to realize, and preparation is simple, it is easy to operation and enforcement, is conducive to industrialized production, has broad application prospects.

Description

A kind of long glass fiber reinforced polypropylene composite material and preparation method thereof
Technical field
The present invention relates to polyacrylic composite and preparation field thereof, be specifically related to a kind of long glass fiber reinforced polypropylene composite material and preparation method thereof.
Background technology
Along with the fast development of national economy, high-performance, low cost thermoplastic resin based composite material are widely applied. By adding fortifying fibre in thermoplastic resin, the technology such as simultaneously resin is modified is to prepare the effective shortcut that fiber-reinforced thermoplastic resin based composites (new structure composite, functional composite material etc.) is new material development. This has become the common recognition of scientific and technological circle, industrial circle, and this is also realize the best-of-breed technology route that general-purpose plastics through engineering approaches, engineering plastics functionalization, special engineering plastics are practical.
Long fiber reinforced thermoplastic composites (LFT) shows than short fiber reinforced composite rigidity more preferably and creep resistant, and its hot strength, bending strength and heat distortion temperature are all high than short fiber reinforced material. Long fiber reinforcement can make the impact strength of composite increase exponentially simultaneously, and remains to, under hot and humid, the mechanical property that maintenance is good.
Long fibre enhanced polypropylene composite (LFT-PP) possesses the mechanical property that short fiber reinforced polypropylene is difficult to reach, its higher stretching, bending strength and modulus have carried out polypropylene general plastic engineering, obtain extensive use at automobile manufacturing field, becoming auto industry and realize the ideal material of low-cost high-efficiency benefit target, one of kind developed by the composite being extremely active in the world at present.
Long fibre enhanced polypropylene composite has higher mechanical strength because of it, it is possible to part replaces PA6(polyamide 6), ABS(acrylonitrile-butadiene-styrene (ABS)), PC(Merlon) etc. engineering material and composite thereof come product or the product of injection moulding different application. But some there are is the product especially nylon refill-unit of environmental adaptation requirement, as automobile steam radiator wind wheel, impeller and electromotor periphery material then need LFT-PP to have good thermostability and heat distortion temperature. The lifting of LFT-PP heat distortion temperature and hot property, can make long fibre enhanced polypropylene composite have broader use scope, be the important indicator realizing polypropylene plastics through engineering approaches.
Owing to long stapled addition makes the various performance of polypropylene all get a promotion, therefore, also occur in that substantial amounts of research paper and report. Wu Weixin, Ren Pu etc. [impact [J] on long glass fiber-reinforced polypropylene performance of the glass form. engineering plastics are applied, 2013,41 (1): 23-26] have studied the different Length of Glass Fiber impact on material mechanical performance, heat distortion temperature and crystal property. Cui Fengbo, Cao Guorong etc. [performance study [J] of glass fiber reinforced polypropylene. glass fibre, 2011, (1): 9-11] compare hot property and the performance of roving glass fiber and short glass fiber RPP. More than research illustrates that fiber glass reinforced polypropylene can be greatly improved polyacrylic heat distortion temperature, but is not directed to improve how further the heat distortion temperature of long glass fiber reinforced polypropylene.
Research paper [beta crystal-type nucleater modified block COPP (PP-B) tube material research [J] .2013 at Bao Guangfu, 34 (1): 28-31] and Chen Meihong et al. paper [OMMT impact [J] on nanometer composite polypropylene material performance. plastics industry, 2011, (5) report the material such as beta crystal-type nucleater, montmorillonite in: 78-81] polyacrylic heat distortion temperature is improved, but be not directed to above material and long glass fibres composite after impact on heat distortion temperature.
Summary of the invention
For improving the heat distortion temperature of long glass fiber reinforced polypropylene composite material, make LFT-PP have broader environmental suitability and have better performance retentivity and stability at a certain temperature, the invention provides a kind of long glass fiber reinforced polypropylene composite material with higher heat distortion temperature.
A kind of long glass fiber reinforced polypropylene composite material, is made up of the raw material of following weight portion:
As preferably, described long glass fiber reinforced polypropylene composite material, it is made up of the raw material of following weight portion:
In the present invention, can combined effect under each component of certain content so that long glass fiber reinforced polypropylene composite material of the present invention has higher heat distortion temperature and excellent mechanical performance. Particularly, synergism can be there is between silane coupler, carborundum, beta crystal-type nucleater and magnesium salt whisker, the heat distortion temperature of long glass fiber reinforced polypropylene composite material of the present invention can be improved so that it is there is the excellent properties such as high temperature resistant, elevated temperature strength is high.
Polypropylene is as matrix material, and can adopt commercially available prod, described polypropylene is one or more different polyacrylic blends of the trade mark in BX3900, K7726, Y2600T, M800HS. Wherein, BX3900 is from SK company of Korea S, and Y2600T, M800HS are that Shanghai Petrochemical Co. Ltd. produces, and K7726 is that yanshan petrochemical company limited produces.
Long glass fibres is in order to RPP material so that it is have good mechanical property.Long glass fibres can adopt commercially available prod, specifically can be selected for the 362J type alkali-free glass fibre direct roving that megalith group produces.
In the present invention, long glass fibres is with common short glass fiber comparatively speaking, in general short glass fiber reinforced polypropylene composite, fibre length is generally less than equal to 1 millimeter, in long glass fiber reinforced polypropylene composite material, the length of fiber is generally higher than 2 millimeters, it it is 2 millimeters～25 millimeters, it is preferred to 2 millimeters～15 millimeters.
Compatilizer is in order to improve the interface compatibility between each component, and compatilizer of the present invention is one or more in PP-MAH graft (PP-g-MAH), polypropylene-acrylic acid-grafted thing (PP-g-MAA), polypropylene-methyl methacrylate-grafted thing (PP-g-MMA). Above-mentioned compatilizer can be effectively improved the problem of Method of Polymer Compatibility difference, changes the polarity of polypropylene material, strengthens the caking property of polymeric matrix and long glass fibres.
Described mineral filler is the one in organo montmorillonite or Pulvis Talci. Wherein organo montmorillonite is the DK1 product that Zhejiang Fenghong New Material Co., Ltd. produces, its XRD interlamellar spacing diffraction maximum 2 θ value is 2.1, it was shown that cheating engaging layer spacing is extended, and extruded effect and melt penetrate into, it is more easy to and makes montmorillonite limellar stripping, thus playing heat rejection effect. Described Pulvis Talci is the 2000 order Pulvis Talci that gold field, Haicheng top grade stone powder factory produces.
Coupling agent can improve mineral filler, carborundum, magnesium salt whisker, long glass fibres etc. and the polyacrylic compatibility. As preferably, described coupling agent is silane coupler, specifically can be selected for Silane coupling agent KH550.
Carborundum has that elastic modelling quantity height, antioxygenic property be superior, high temperature resistant and the excellent properties such as elevated temperature strength is high, has the carborundum filled polypropylene of certain crystal habit, is demonstrated by the enhancing function of excellence.
Alpha-crystal form in polypropylene can be converted into beta crystal by beta crystal-type nucleater, and plays the effect refining spherocrystal, enhances the intensity of PP and improves the heat distortion temperature of PP. Described beta crystal-type nucleater is one or more in the beta crystal-type nucleater of model TMB-5, BNu-100, PCM40A. Wherein, TMB-5 is purchased from Shanxi-Prov Inst of Chemical Industry, and BNu-100 is purchased from Tianjin Tian Ji scientific & trading Co., Ltd., and PCM40A is purchased from Mitsubishi Chemical (China).
Polypropylene processing flowing difference can be caused owing to increasing polypropylene with long glass fibres, magnesium salt whisker filled polypropylene material, magnesium salt whisker and long glass fibres can be mingled in polypropylene matrix well and play the collaborative effect strengthened, improve mechanical property and the hot property of material. Described magnesium salt whisker is one or more in alkali magnesium sulfate, magnesium borate crystal whisker.
Owing to magnesium salt whisker is generally inorganic magnesium salt whisker, for solid powder, volume is fluffy, and bulk density is low, and therefore, after coupling agent treatment, magnesium salt whisker can be coated with well by matrix resin, forms good boundary layer with matrix resin.
As preferably, described processing aid is the component of the following weight portion in polypropylene 100 parts:
Lubricant 0～5 part;
0～5 part of antioxidant;
It is preferred that, described processing aid is the component of the following weight portion in polypropylene 100 parts:
Lubricant 0.6～3 part;
0.6～3 part of antioxidant.
Wherein, described lubricant is Tissuemat E (PE wax).The friction added between the minimizing internal friction of strand, melt and mineral of lubricant, reduces viscosity, thus improving fluidity of molten.
For suppressing or delaying polypropylene oxidative degradation in processing and use procedure, polyacrylic modifying process needs add antioxidant, and the polymer of different structure has different oxidation resistances, in the present invention, described antioxidant is at least two in antioxidant 1010, antioxidant 1076, irgasfos 168, antioxidant DSTP.
The preparation method that present invention also offers a kind of long glass fiber reinforced polypropylene composite material, its preparation is simple, workable, it is easy to industrializing implementation produces.
The preparation method of a kind of long glass fiber reinforced polypropylene composite material, comprises the following steps:
The coupling agent of partial amount is mixed 10min～30min with 500～1500 revs/min with mineral filler in mixer, makes mineral activation, obtain the mineral filler modifiied;
The coupling agent of partial amount is mixed 10min～30min with 500～1500 revs/min with carborundum in mixer, obtains the carborundum modifiied;
The coupling agent of partial amount is mixed 10min～30min with 500～1500 revs/min with magnesium salt whisker in mixer, obtains the magnesium salt whisker modifiied;
Polypropylene, compatilizer, the coupling agent of surplus, modified mineral filler, modified carborundum, modified calcium salt whisker and the alternative processing aid added are added double screw extruder from feeding feed bin after 2000～4000 revs/min of mixed at high speed 0.5～5min in homogenizer;
The head of double screw extruder is connected with long glass fibres impregnation mold, and long glass fibres is through impregnation with mould and merges with melt polypropylene, and water cooled, pelletizing obtains long glass fiber reinforced polypropylene composite material.
Wherein, joining each raw material components amount of homogenizer and measured by weighing balance, long glass fibres measures the amount of long glass fibres by traction apparatus rotating speed, thus reaching the composite of different long glass fibres content. Pull out the composite of impregnation mold, water cooled, pelletizing, obtain the long glass fiber reinforced polypropylene composite material that particle diameter is 10～15mm, for pellet.
The described double screw extruder the first temperature section from feed zone to head is set as 160 DEG C～180 DEG C, 180 DEG C～200 DEG C, 200 DEG C～220 DEG C, 220 DEG C～240 DEG C, 240 DEG C～260 DEG C, 240 DEG C～260 DEG C, 240 DEG C～260 DEG C, 240 DEG C～260 DEG C to the temperature of the 8th temperature section; The temperature of impregnation mold is 240 DEG C～260 DEG C.
Compared with prior art, present invention have the advantage that
Long glass fiber reinforced polypropylene composite material of the present invention has higher heat distortion temperature, can use and have stability and property retention in broader temperature range. The heat distortion temperature under long glass fiber reinforced polypropylene composite material winding degree 1.82Mpa in the present invention at 160-163 DEG C, the heat distortion temperature under winding degree 0.45Mpa at 162-168 DEG C, the closely melt temperature Tm of polypropylene material. And generally the heat distortion temperature under winding degree 1.82Mpa of the long glass fiber reinforced polypropylene composite material under equal long glass fibres content of ashes is about 150 DEG C, such as ticonaPP-GF30-04 heat distortion temperature under 1.82Mpa is 148 DEG C, RTPimagineering105CC heat distortion temperature under winding degree 1.82Mpa is 141 DEG C, and the heat distortion temperature under winding degree 0.45Mpa is 157 DEG C.The heat distortion temperature of long glass fiber reinforced polypropylene composite material of the present invention can form competition contrast with general nylon modified materials and polycarbonate modified material. Meanwhile, long glass fiber reinforced polypropylene composite material of the present invention has the mechanical property of excellence, is conducive to promoting the use of of this material.
The preparation method of long glass fiber reinforced polypropylene composite material of the present invention, adopts existing double screw extruder to realize, and preparation is simple, it is easy to operation and enforcement, is conducive to industrialized production, has broad application prospects.
Detailed description of the invention
Embodiment 1～4 and comparative example 1～4
Long glass fiber reinforced polypropylene composite material, as shown in Table 1 and Table 2, unless otherwise indicated, part refers to weight portion to the proportioning raw materials of embodiment 1～4 and comparative example 1～4.
The preparation method of long glass fiber reinforced polypropylene composite material, comprises the following steps:
The coupling agent of 1/5th weight portions is mixed 20min with 1000 revs/min with mineral filler in mixer, obtains the mineral filler modifiied;
The coupling agent of 1/5th weight portions is mixed 20min with 1000 revs/min with carborundum in mixer, obtains the carborundum modifiied;
The coupling agent of 1/5th weight portions is mixed 20min with 1000 revs/min with magnesium salt whisker in mixer, obtains the magnesium salt whisker modifiied;
By polypropylene, compatilizer, the coupling agent of 2/5ths weight portions, modified mineral filler, modified carborundum, modified magnesium salt whisker and the alternative processing aid added add double screw extruder from feeding feed bin by weighing balance after homogenizer high speed (rotating speed 3000RPM) mixes 1min, the head of double screw extruder is connected with long glass fibres impregnation mold, long glass fibres is through impregnation with mould and merges with melt polypropylene, pull out the composite of impregnation mold, through room temperature (namely under ambient temperature) water-cooled, pelletizing, room temperature (namely under ambient temperature) water-cooled, obtain long glass fiber reinforced polypropylene composite material, this material is pellet, diameter is 2～4mm, length is 11～12mm. wherein, the double screw extruder the first temperature section from feed zone to head is set as 160 DEG C～180 DEG C, 180 DEG C～200 DEG C, 200 DEG C～220 DEG C, 220 DEG C～240 DEG C, 240 DEG C～260 DEG C, 240 DEG C～260 DEG C, 240 DEG C～260 DEG C, 240 DEG C～260 DEG C to the temperature of the 8th temperature section. the temperature of impregnation mold is 240 DEG C～260 DEG C. in long glass fiber reinforced polypropylene composite material, the length of fiber is 2 millimeters～5 millimeters.
Table 1
Table 2
Wherein, PP-g-MAA list of references (Huang Cipei, Zhang Wengen etc., Graft copolymerization of acrylic acid onto isotactic polypropylene, synthetic resin and plastics, 2001,18(6): 4～9) prepare.
Prepared by PP-g-MMA list of references (Lin Shuidong, woods will are brave, the PP-g-MMA research to cloud model controller system compatibilization, functional material, 9 phases in 2005).
The long glass fiber reinforced polypropylene composite material retable molding of embodiment 1～4 and comparative example 1～4 preparation, measures mechanical property, and its result is as shown in Table 3 and Table 4.
Table 3
Performance project Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Hot strength Mpa 124.6 118 138 112.3
Bending strength Mpa 145.8 113.1 167.4 140.4 7 -->
Bending modulus Mpa 5560 5254.8 8066.2 7303.2
Simply supported beam notch shock kJ/m2 29.2 17.3 30.2 16.4
The non-notch shock kJ/m of simply supported beam2 50 39.4 51 40.7
HDT0.45Mpa℃ 167 162 168 165
HDT1.8Mpa℃ 161 160 163 162
Table 4
Performance project Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Hot strength Mpa 100 124 115 113
Bending strength Mpa 156 154 138 146
Bending modulus Mpa 7053 7853.5 7100 7075
Simply supported beam notch shock kJ/m2 25 28.3 26.3 26.1
The non-notch shock kJ/m of simply supported beam2 43 43 44 43
HDT0.45Mpa℃ 155 156 154 153
HDT1.8Mpa℃ 151 153 150 150
Compared with embodiment 3, comparative example 1 does not add coupling agent, the non-plus silicon carbide of comparative example 2, and comparative example 3 does not add beta crystal-type nucleater, and comparative example 4 does not add magnesium salt whisker, and all the other are all identical with embodiment 3.From performance detection data, comparative example 1～4 is all not as embodiment 3, visible, in the present invention, synergism can be there is between silane coupler, carborundum, beta crystal-type nucleater and magnesium salt whisker, the heat distortion temperature of long glass fiber reinforced polypropylene composite material of the present invention can be improved so that it is there is the advantages such as high temperature resistant, excellent in mechanical performance.

Claims (6)

1. a long glass fiber reinforced polypropylene composite material, it is characterised in that be made up of the raw material of following weight portion:
Described mineral filler is the one in organo montmorillonite or Pulvis Talci.
2. long glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that, described compatilizer is one or more in PP-MAH graft, polypropylene-acrylic acid-grafted thing, polypropylene-methyl methacrylate-grafted thing.
3. long glass fiber reinforced polypropylene composite material according to claim 1, it is characterised in that described coupling agent is silane coupler.
4. long glass fiber reinforced polypropylene composite material according to claim 1, it is characterised in that described magnesium salt whisker is one or both in alkali magnesium sulfate, magnesium borate crystal whisker.
5. long glass fiber reinforced polypropylene composite material according to claim 1, it is characterised in that described processing aid is the component of the following weight portion in polypropylene 100 parts:
Lubricant 0～5 part;
0～5 part of antioxidant.
6. long glass fiber reinforced polypropylene composite material according to claim 5, it is characterised in that described lubricant is Tissuemat E;
Described antioxidant is at least two in antioxidant 1010, antioxidant 1076, irgasfos 168, antioxidant DSTP.
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