CN104910517A - Bimodally-distributed glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Bimodally-distributed glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 66
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 58
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 58
- -1 polypropylene Polymers 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 28
- 230000002902 bimodal effect Effects 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 32
- 238000005520 cutting process Methods 0.000 claims description 26
- 238000012360 testing method Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- VKLYZBPBDRELST-UHFFFAOYSA-N ethene;methyl 2-methylprop-2-enoate Chemical compound C=C.COC(=O)C(C)=C VKLYZBPBDRELST-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 241000143437 Aciculosporium take Species 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 230000002787 reinforcement Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000011152 fibreglass Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 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
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- 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
- C08L23/14—Copolymers of propene
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- 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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- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a bimodally-distributed glass fiber reinforced polypropylene composite material and a preparation method thereof, belonging to the technical field of high polymer materials. The bimodally-distributed glass fiber reinforced polypropylene composite material comprises the following raw materials in percentage by weight: 40%-70% of polypropylene, 3%-10% of a graft compatilizer, 20%-40% of a glass fiber chopped felt, 10%-30% of glass fiber powder and 3%-10% of an olefin elastomer. The bimodally-distributed glass fiber reinforced polypropylene composite material has the superiorities; by adding and compounding glass fiber reinforcement bodies of different lengths, a specific composite reinforcing system in which glass fiber lengths are of a bimodal distribution effect is built in polypropylene, the structural and performance differences of traditional glass fiber reinforced polypropylene in the longitudinal direction and the transverse direction are changed, the mechanical performance and thermal performance of the material in a vertical flow direction are remarkably improved.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to glass fiber reinforced polypropylene composite material of a kind of bimodal distribution and preparation method thereof.
Background technology
Polypropylene has excellent over-all properties because of it, good chemical stability, the price of good forming process type and relative moderate and be able at automobile, electrical equipment, each field such as building materials widely uses, it is one of maximum general-purpose plastics kind of current consumption, but pile up because its molecular chain is easily regular, thus cause the molding shrinkage of gained product large, size fluctuation is obvious, therefore, add inorganic reinforcement such as glass fibre GF and can not only effectively make up polyacrylic performance deficiency, and be also conducive to the forming process problem improving polypropylene material, long glass fiber-reinforced polypropylene materials is exactly the most typical in application case, to be used in passenger car some secondary structure parts as front end frame, instrument board framework, vehicle door interior trim panel, centre gangway skeleton, the important structural element such as skylight sash embodies the " environmental protection of contemporary automotive industry, lightweight " development trend.
The patent No. is CN201210057816.9, publication number be the Chinese patent application of CN102604216A a kind of can fiber glass reinforced polypropylene composition and method of making the same and the application of laser labelling disclose a kind of can the fiber glass reinforced polypropylene composition of laser labelling, it is characterized in that, comprise following component by mass percentage: acrylic resin 40-80%; Elastomerics 5-30%; Glass fibre 5-50%; Compatilizer 0.01-10%; Black toner 0.01-3%; Other additives 0.01-5%.Its preparation method is: the above-mentioned each component except glass fibre be mixed in proportion, by twin screw extruder or the main spout charging of reciprocating single-bolt extruder, glass fibre is by side spout charging, melting mixing 0.1 ~ 5min at 200 ~ 280 DEG C, screw slenderness ratio is not less than 32 ~ 66, extrude pelletizing and get final product, it is advantageous that and add the good material of electroconductibility, be used for improving nonpolar glass fiber reinforced polypropylene composite material surface property, but do not promote mechanical property and the dimensional stability of matrix material.
For the short glass fiber reinforced polypropylene compound material of routine, because the distribution length of its reinforcement is not as good as roving glass fiber material, therefore, polyacrylic dimensional stability is improved and does not give prominence to, and when injection moulding, glass fibre because of length shorter, easily find the orientation dispersion of streamwise, thus cause the structure of matrix material on perpendicular flow direction and performance issue.Not only the mechanical performance index of material is on the low side, and shrinking percentage is bigger than normal, easily produce fluctuation with the change of envrionment temperature.Research display, for the short glass fiber reinforced polypropylene compound material of routine, about 70% glass of its material internal is all distributed within the length range of 0.6 ~ 0.9mm, there is the length-to-diameter ratio of quite high (1:40 ~ 1:70), if the fiberglass reinforced body that length-to-diameter ratio is lower can be introduced, the integrated distribution peak of another glass is constructed in the scope of 0.2 ~ 0.4mm, the anisotropic problem improving polypropylene composite material will be contributed to, promote the material property on perpendicular flow direction and dimensional stability.
Summary of the invention
(i.e. bimodal distribution) glass fiber reinforced polypropylene composite material that the invention provides a kind of modification and preparation method thereof, felt is cut by add glass fiber powder that length-to-diameter ratio is 1:10 ~ 1:50mm and length be that the glass of 3 ~ 4.5mm is short, coordinate suitable interface modification compatilizer, at the glass fiber reinforcements that a kind of length distribution of polypropylene composite material internal build is bimodal morphology, alleviate the structure and property anisotropy that cause because of the one-dimension oriented distribution of glass fibre, make the glass fiber reinforced polypropylene composite material obtained at flow direction, the mechanical property in perpendicular flow direction all can remain on higher level, meet the relevant interior/exterior material standard of performance of main engine plants.
Wherein bimodal distribution refers to by the fiberglass reinforced body of different lengths composite, and the Fiber Distribution curve of matrix material constructs the region of 0.15 ~ 0.3mm, 0.6 ~ 0.8mm, two glass integrated distribution.
The object of the invention is to be achieved through the following technical solutions:
A glass fiber reinforced polypropylene composite material for bimodal distribution, comprises the raw material of following weight percent:
Wherein, described polypropylene be homo-polypropylene (molecular weight 80000 ~ 10000), Co-polypropylene (molecular weight 100000 ~ 120000) one or both, 230 DEG C, under the test condition of 2.16Kg, its melting index is 5 ~ 30g/min; Preferred crystallinity Xc >=99.5% of homo-polypropylene, SK Chemical of Korea S; Preferred crystallinity Xc >=99.5% of Co-polypropylene, SK Chemical of Korea S.
Described grafts compatilizer is maleic anhydride inoculated polypropylene compatilizer 5001-C, and its percentage of grafting is 0.5 ~ 3% through chemical titration test, commercially available, rises novel material company limited purchased from Nantong day.
Described short glass fiber is short, and to cut felt be that continuous glass fibre folded yarn is short cuts rear gained, and the short felt filament diameter of cutting of short glass fiber is 13um, and chopped length is 3 ~ 4.5mm; Preferred Mount Taishan glass.
The described glass fiber powder gained that is continuous glass fibre precursor after shortly cutting, grinding screening, its diameter is 10um, and after grinding, the length-to-diameter ratio of fiber powder is 10 ~ 50; Commercially available, purchased from Nanjing Hao Cheng matrix material company limited.
Described olefin type elastomer refers to ethylene methyl methacrylate segmented copolymer, 190 DEG C, melting index 0.5 under 2.16Kg test condition, and the ethylene methyl methacrylate segmented copolymer of preferred purchased from American E.I.Du Pont Company.
The preparation method of the glass fiber reinforced polypropylene composite material of above-mentioned bimodal distribution, comprises the following steps:
(1) take polypropylene, grafts compatilizer, glass fiber powder and olefin type elastomer by described weight percent, mix, obtain mixing raw material;
(2) dried mixing raw material is positioned in the main feeding bin of tight meshing co rotating twin screw extrusion, join in the machine barrel of forcing machine through feed screw, short for glass felt of cutting is joined forcing machine from side spout, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, engine speed is 250 revs/min, through melt extruding, cooling, granulation, obtains product after the operation such as drying and processing.
Beneficial effect
By the reinforced polypropylene compound material that technical scheme of the present invention prepares, lay particular emphasis on the composite structure and performance that cause because of the one-dimension oriented characteristic of reinforcement glass fibre at flow direction, the significant difference in perpendicular flow direction, composite by the fiberglass reinforced body of different lengths, the Fiber Distribution curve of matrix material constructs 0.15 ~ 0.3mm, the region of 0.6 ~ 0.8mm, two glass integrated distribution, Material reinforcement system is uniformly dispersed, distribution rationally, significantly improve the performance deficiency of glass fiber reinforced polypropylene composite material on perpendicular flow direction, simultaneously, the dimensional stability of the glass fiber reinforced polypropylene composite material of gained is also taken on a new look to some extent, in envrionment temperature from low temperature (-30 DEG C) to the process that high temperature (-120 DEG C) changes, material is at flow direction, coefficient of linear expansion on perpendicular flow direction remains within rational gap scope, this characteristic is to being applied to front end frame, skylight sash, particularly crucial during the vehicle structure parts such as door internal decoration plate.
The tensile strength on perpendicular flow direction of gained matrix material, flexural strength comparatively traditional material raising 30% ~ 50%, and material is in the temperature range of-30 ~ 120 DEG C, it longitudinally, comparatively conventional material is more close for horizontal coefficient of linear expansion, shows that resulting materials has better size and mechanical property hold facility in different envrionment temperatures.
Embodiment
Below by concrete embodiment, the present invention is described further, and described embodiment is only for illustration of the present invention instead of limitation of the present invention.
The embodiment of the present invention is raw materials used:
PP-1: homo-polypropylene, crystallinity Xc >=99.5%, SK Chemical of Korea S, melting index 20g/min (230 DEG C, 2.16Kg).
PP-2: Co-polypropylene, crystallinity Xc >=96.5%, SK Chemical of Korea S, melting index 10g/min (230 DEG C, 2.16Kg).
PP-3: homo-polypropylene, crystallinity Xc >=96.5%, SK Chemical of Korea S, melting index 5g/min (230 DEG C, 2.16Kg).
PP-4: Co-polypropylene, crystallinity Xc >=96.5%, SK Chemical of Korea S, melting index 30g/min (230 DEG C, 2.16Kg).
Grafts compatilizer-1: maleic anhydride MAH graft polypropylene CMG5001-C, chemical titration test percentage of grafting is 1.0%, commercially available, rises novel material company purchased from Nantong day.
Grafts compatilizer-2: maleic anhydride MAH graft polypropylene CMG9801, chemical titration test percentage of grafting is 0.5%, commercially available, rises novel material company purchased from Nantong day.
Grafts compatilizer-3: maleic anhydride MAH graft polypropylene GPM200A, chemical titration test percentage of grafting is 3%, purchased from the light novel material company of Ningbo energy.
Short glass fiber is short cuts felt-1: continuous glass fibre folded yarn is short cuts felt, diameter 13um, chopped length 4.5mm, Mount Taishan glass.
Short glass fiber is short cuts felt-2: continuous glass fibre folded yarn is short cuts felt, diameter 13um, chopped length 3mm, Mount Taishan glass.
Glass fiber powder-1: continuous glass fibre precursor folded yarn is short to be cut, it is rear obtained to grind, and diameter 10um, staple length is 0.1mm, purchased from Nanjing Hao Cheng matrix material company limited.
Glass fiber powder-2: continuous glass fibre precursor folded yarn is short to be cut, it is rear obtained to grind, and diameter 10um, staple length is 0.5mm, purchased from Hangzhou high-tech matrix material company limited.
Olefin type elastomer: ethylene methyl methacrylate segmented copolymer, du pont company, melting index 0.5 (190 DEG C, 2.16Kg).
Product performance are tested:
Prepared by standard batten: after the reinforced polypropylene compound material particle of gained is dried 6 ~ 8h, in double-screw injection molding machine, be injected into the model of size 356 × 100 × 4mm, then on sanction model machine, in the both direction of flowing (∥), perpendicular flow (⊥), cut standard testing batten by ISO Mechanics Performance Testing standard.
Tensile property: undertaken by ISO527-2 standard, test rate is 5mm/min.
Bending property: undertaken by ISO178 standard, span is 64mm, and test rate is 2mm/min.
Impact property: carry out on impact tester for simple supported beam by ISO179-1 standard, batten non-notch.
Coefficient of linear expansion: undertaken by the method shown in ISO11359-2 standard, selection standard tensile bars, be positioned in thermodynamic analyzer TMA, test in-30 DEG C ~ 120 DEG C temperature ranges, standard batten is temperature variant dimensional change situation in flowing (∥), perpendicular flow (⊥) both direction, after converting, obtain matrix material thermal linear expansion coefficient in the two directions.
Embodiment 1
Each component is taken by embodiment 1 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
The formula table of the glass fiber reinforced polypropylene composite material of table 1 bimodal distribution (unit: gram)
Embodiment 2
Each component is taken by embodiment 2 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Embodiment 3
Each component is taken by embodiment 3 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Embodiment 4
Each component is taken by embodiment 4 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Embodiment 5
Each component is taken by embodiment 5 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Embodiment 6
Each component is taken by embodiment 6 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Embodiment 7
Each component is taken by embodiment 7 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Embodiment 8
Each component is taken by embodiment 8 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Comparative example 1
Each component is taken by comparative example 1 data shown in table 1, short for glass each component of cutting beyond felt is mixed with high-speed mixer, put in the main feeding bin of twin screw extruder, side feeding bin put into by the short felt of cutting of glass, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 250 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
The performance of the glass fiber reinforced polypropylene composite material of table 2 bimodal distribution and structured testing result
According to the performance test results of each embodiment shown in table 2, comparative example, and physical property formula in contacts list 1 in general, in gained fiber glass reinforced polypropylene material, adopts the composite property of homo-polypropylene to be obviously better than co-polypropylene, the total content of glass fiber reinforcements and ratio need control in suitable ratio, glass is short cut felt too high levels (embodiment 8) then matrix material there is good mechanical property, but the indicator difference in level, perpendicular flow both direction is larger, be unfavorable for the dimensional stability of matrix material, the performance of glass fiber powder too high levels then matrix material can be seriously impaired, contrast each embodiment further then known, the total content of glass fiber reinforcements controls within the interval of 30 ~ 40%, the technical scheme that glass fiber powder/short ratio of cutting felt to be 1:2 be effect is ideal, the test result of reinforced polypropylene compound material as described in Example 4, its fiberglass reinforced body total content is 35%, not only flow direction stretches, flexural strength remains on ideal numerical value, the more important thing is, material property conservation rate on its perpendicular flow direction all likes more than 85%, and in comparative example 1, the mechanical property conservation rate of matrix material on perpendicular flow direction is only 70% even lower., also can find, the composite fiberglass reinforced system of this length is also helpful to improving the impact property of material on flowing, perpendicular flow two direction meanwhile.
The coefficient of linear expansion CLTE tested in the flowing of polypropylene composite material, perpendicular flow both direction by thermodynamics analysis method TMA is known, conventional fiber glass reinforced polypropylene material (comparative example 1) is in low temperature, normal temperature, hot environment, CLTE numerical difference on two direction can reach more than 10 times, CLTE numerical difference then can be reduced to about 2 to 3 times by the fiberglass reinforced system adopting length composite, shows that the dimensional stability of matrix material has clear improvement.By known to the glass fibre length distribution tests of polypropylene material, the short use-pattern of cutting felt of glass fiber powder collocation, the fortifying fibre integrated distribution of gained matrix material is in 0.15 ~ 0.3mm, in two narrower intervals of 0.6 ~ 0.8mm, present unique bimodal distribution state, wherein, the anisotropy of matrix material can be improved in the glass areal concentration (0.15 ~ 0.3mm) that length is lower, and the higher glass areal concentration (0.6 ~ 0.8mm) of length can ensure that polypropylene composite material still has higher mechanical property, to meet the main engine plants of current joint brand as masses, Ford, general grade is about front end frame, door internal decoration plate, the associated materials standard of boot spare tyre and sound set stent isostructuralism parts, ensure the finished parts performance test of gained product in the later stage, all desirable performance can have been given play in component assembly test, positive cooperation Ge great main engine plants advance the lightweight of car industry " to mould Dai Gang ", the process of environmental protection, create good Social benefit and economic benefit.
Claims (7)
1. a glass fiber reinforced polypropylene composite material for bimodal distribution, is characterized in that: the raw material comprising following weight percent:
2. the glass fiber reinforced polypropylene composite material of a kind of bimodal distribution according to claim 1, it is characterized in that: described polypropylene be homo-polypropylene, Co-polypropylene one or both, 230 DEG C, under the test condition of 2.16Kg, its melting index is 5 ~ 30g/min, homo-polypropylene molecular weight 80000 ~ 100000, Co-polypropylene molecular weight 100000 ~ 120000.
3. the glass fiber reinforced polypropylene composite material of a kind of bimodal distribution according to claim 1, is characterized in that: described grafts compatilizer is maleic anhydride inoculated polypropylene compatilizer, and its percentage of grafting is 0.5 ~ 3% through chemical titration test.
4. the glass fiber reinforced polypropylene composite material of a kind of bimodal distribution according to claim 1, it is characterized in that: described short glass fiber is short, and to cut felt be that continuous glass fibre folded yarn is short cuts rear gained, the short felt filament diameter of cutting of short glass fiber is 13um, and chopped length is 3 ~ 4.5mm.
5. the glass fiber reinforced polypropylene composite material of a kind of bimodal distribution according to claim 1, it is characterized in that: the described glass fiber powder gained that is continuous glass fibre precursor after shortly cutting, grinding screening, continuous glass fibre precursor diameter is 10um, and the length-to-diameter ratio of fiber is 10 ~ 50.
6. the glass fiber reinforced polypropylene composite material of a kind of bimodal distribution according to claim 1, it is characterized in that: described olefin type elastomer refers to ethylene methyl methacrylate segmented copolymer, 190 DEG C, melting index 0.5 under 2.16Kg test condition.
7. the preparation method of the glass fiber reinforced polypropylene composite material of bimodal distribution according to claim 1, is characterized in that, carries out according to following steps:
A. take polypropylene, grafts compatilizer, glass fiber powder and olefin type elastomer by described weight percent, mix, obtain mixing raw material;
B. dried mixing raw material is positioned in the main feeding bin of tight meshing co rotating twin screw extrusion, join in the machine barrel of forcing machine through feed screw, short for glass felt of cutting is joined forcing machine from side spout, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, each zone temperature of main barrel exports and is set as from charging opening to head: 60 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, engine speed is 250 revs/min, through melt extruding, cooling, granulation, obtains product after the operation such as drying and processing.
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