CN104710687B - Fibre reinforced polypropylene resin composite with excellent molded feature - Google Patents
Fibre reinforced polypropylene resin composite with excellent molded feature Download PDFInfo
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- CN104710687B CN104710687B CN201410488174.7A CN201410488174A CN104710687B CN 104710687 B CN104710687 B CN 104710687B CN 201410488174 A CN201410488174 A CN 201410488174A CN 104710687 B CN104710687 B CN 104710687B
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- acrylic resin
- carbon fiber
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- modified polypropene
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 93
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 88
- -1 polypropylene Polymers 0.000 title claims abstract description 63
- 239000000835 fiber Substances 0.000 title claims abstract description 41
- 239000000805 composite resin Substances 0.000 title claims abstract description 32
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 56
- 239000004917 carbon fiber Substances 0.000 claims abstract description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 38
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 38
- 239000004067 bulking agent Substances 0.000 claims abstract description 27
- 238000000465 moulding Methods 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 15
- 239000011347 resin Substances 0.000 description 37
- 229920005989 resin Polymers 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 239000012783 reinforcing fiber Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000002708 enhancing effect Effects 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000985630 Lota lota Species 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides the fibre reinforced polypropylene resin composite with improved molding performance.Specifically, by be used as modified polypropene that the maleic anhydride of bulking agent is grafted to acrylic resin addition to enhance carbon fiber, the fibre reinforced polypropylene resin composite with molding performance, tensile strength, bending strength for significantly improving etc. is provided.
Description
Technical field
The present invention relates to the fibre reinforced polypropylene resin composites with improved molded feature.Specifically, pass through
The modified polypropene being grafted through maleic anhydride as bulking agent is added to enhance carbon fiber to acrylic resin, and can prepare has
The fibre reinforced polypropylene resin composite of the molded feature, tensile strength, the bending strength that significantly improve etc..
Background technology
In general, including polypropylene is widely used in various engineering plastics as the resin combination of basic resin and answers
With.
For the physical characteristic of reinforced polypropylene resin combination, by mixing reinforcing fiber etc. with resin combination
And fibre-reinforced compound is prepared, and the compound has been used for related field.Due to compared with typical engineering plastics this
The resin complexes of kind fiber reinforced polypropylene have improved physical characteristic such as rigidity and heat resistance, therefore resin complexes
Especially it is widely used as functional engineering plastics in automotive field, power industry field etc. in various industrial circles.However,
There are still problems for other physical characteristics, therefore, it is necessary to continue to make improvement.
In the related art, it has been introduced into the forming method of fiber reinforced thermoplastic resin and forms equipment.For example, having drawn
Enter the composite material including glass fibre.
Currently, fiber reinforced polypropylene resin composition may be one kind in most widely used resin, pass through use
Such as the reinforcing fiber of glass fibre or carbon fiber carrys out filled polypropylene resin and has the rigidity or heat resistance enhanced.This it
In, in order to improve the compatibility of acrylic resin and reinforcing fiber, by by improved polyalkene be added to acrylic resin come
Physical characteristic such as rigidity and heat resistance needed for improving, to increase its compatibility with reinforcing fiber, wherein can be by by horse
Carry out sour wait and prepares improved polyalkene with polypropylene grafted.For example, have now been developed including by addition polypropylene and maleic acid and
The sour modified polypropene of generation and the composition of carbon fiber；And it has been reported that include the polypropylene of 100 parts by weight, 10 to 50
The resin group of the conductive black of the maleated polypropylene of parts by weight, the carbon fiber of 5 to 65 parts by weight and 5 to 65 parts by weight
Close object.In addition, it has been suggested that the maleic anhydride modified polypropylene tree of polypropylene, 0.5 to 20 parts by weight including 100 parts by weight
The resin combination of fat, carbon fiber or carbon black, glass fibre and inorganic filler.Although above-mentioned polypropene composition may have
Excellent rigidity and heat resistance, but they cannot be used for being subjected to external punching because of its lower tensile strength and bending strength
The component hit.Therefore, aforementioned conventional polypropene composition may have poor impact energy absorbability, and work as its quilt
It is broken when moulding product such as damper, buffer, bumper (bumper), external component and other internal parts for vehicle
It splits.
Some effort have been made for example by adding rubber components or improving physical characteristic using specific polypropylene.So
And due to specific polypropylene, compared with improved other physical characteristics such as rigidity, in tensile strength or impact absorbing ability etc.
The improvement of aspect is insufficient, therefore, not yet solves the problems, such as to generate faulty goods.
In other instances, have now been developed will be that (NMR is with reference to mark by 87wt% to 92wt% with isotactic index
It is accurate) and propylene monomer that melt index (MI) is 0.5 to 35g/10min (230 DEG C) as polypropylene base resin simultaneously using rubber
The specific use of elastomer, but composition fails to solve the problems, such as that tensile strength or bending strength etc. are bad.
The above-mentioned information disclosed in the background technology part is only used for strengthening the understanding to background of the present invention, therefore it may
Containing do not constitute state those skilled in the art it is known that the prior art information.
Invention content
The present inventor can provide the solution of the above problem in related field.Specifically, when with specific object
The acrylic resin of reason characteristic is used as basis material；Maleic anhydride modified polypropylene and bulking agent melt kneading；And it is impregnated with
When carbon fiber, propylene resin composition can have improved physical characteristic, such as molded feature, tensile strength, bending strength etc..
In one aspect, the present invention provides a kind of polypropylene resin composite, and molded feature and physical characteristic are for example drawn
Stretching intensity and bending strength can be enhanced.Specifically, the fibre reinforced polypropylene tree with improved molded feature is provided
Oil/fat composition, wherein carbon fiber can be immersed in polypropylene.Have because thermoplastic resin penetrates into carbon fiber in addition, the present invention is provided
There is the fibre reinforced acrylic resin compound of improved carbon fiber distribution and mechanical property.
On the other hand, the present invention also provides a kind of molding products, and the molding product is by using with improvement
The fibre reinforced polypropylene resin composite of molded feature is moulded and is made.
In the exemplary embodiment, polypropylene resin composite may include：Content is about 50wt% to about 80wt%
As Noblen or the acrylic resin of propylene-ethylene copolymers, it is about 20g/ to have at a temperature of about 230 DEG C
The melt index (MI) (MI) of 10min to about 100g/10min, the molecular weight distribution (MWD) of about 5 to about 10 and about 97 to about 100 it is complete
With vertical structure index；Content, which is about 1wt% to about 10wt%, as bulking agent has about 0.5wt% to the Malaysia of about 15wt%
The modified polypropene of acid anhydrides grafting rate；And about 15wt% is to the carbon fiber of about 40wt%.
It should be appreciated that unless otherwise specified, the weight percent of resin combination is to be based on as disclosed herein
The total weight of resin combination.
In the exemplary embodiment, can by will about 15wt% to the amount of about 40wt% impregnated carbon fiber it is mixed in melting
It closes and prepares fibre reinforced acrylic resin compound in object, it is about 50wt% to about that wherein molten mixture, which includes content,
The acrylic resin and content as Noblen or propylene-ethylene copolymers of 80wt% is about 1wt% to about 10wt%
The modified polypropene as bulking agent.Specifically, it at a temperature of about 230 DEG C is about 20 to about that acrylic resin, which can have,
The melt index (MI) (MI) of 100g/10min, the molecular weight distribution (MWD) of about 5 to about 10 and the isotaxy of about 97 to about 100 refer to
Number.In addition, modified polypropene can be with the maleic anhydride grafting ratio of about 0.5wt% to about 15wt%.
In the exemplary embodiment, the present invention also provides a kind of molding products, and the molding product is by using polypropylene
Resin combination is moulded and is made.
The fibre reinforced polypropylene resin composite of each illustrative embodiments according to the present invention can be with various sides
Formula is used as engineering plastics, because resin combination can have improved rigidity or different mechanical strength and can also be with low
Melt viscosity and improved molded feature, elasticity modulus etc..Specifically, by using above-mentioned allyl resin and with as bulking agent
Maleic anhydride grafting modified polypropene, can get the physical characteristic such as tensile strength and bending strength that significantly improve.
In addition, because during preparing carbon fiber composite, allyl resin can have improved intensity and mobility
And it can be easily penetrate into carbon fiber bundle, so can get the additional effect of the physical characteristic enhancing caused by dispersibility improves
Fruit.In addition, when component is moulded through injection molding or extrusion forming process, machinability can be improved and can also reduce cycle
Time, to enhance presentation quality.
Therefore, when allyl resin is applied to various industrial products, or specifically when PP resins are applied to vehicle portion
When part, physical characteristic can be significantly improved.
In addition, because can get under relatively low carbon fiber content and a small amount of expensive carbon fibre material required strong
Degree, so the technology provided in the present invention can reduce material cost.
Other aspects of the present invention and each illustrative embodiments are discussed below.
Description of the drawings
The above and other feature of the present invention is carried out referring now to the illustrative embodiments illustrated in the accompanying drawings detailed
It describes these bright, described below embodiments in detail to merely exemplify, therefore is not limitation of the present invention, wherein：
Fig. 1 is the example process being immersed in reinforcing fiber in resin shown according to exemplary embodiment of the invention
Schematic diagram；
Fig. 2 is shown according to an illustrative embodiment of the invention when usable typical leaching in the dipping process in Fig. 1
The schematic diagram of exemplary internal structure when stain mold；And
Fig. 3 shows the microgram of the rupture cross section of the exemplary tensile sample of acrylic resin compound.Fig. 3 (a) be
The microgram of the rupture cross section of the polypropylene resin composite prepared in comparative example 2；And Fig. 3 (b) is example according to the present invention
The microgram of the rupture cross section of property embodiment in example 2.Microgram is captured by scanning electron microscope (SEM).
It should be appreciated that appended attached drawing is not necessarily in proportion, and the basic principle for illustrating the present invention is only presented
The a degree of of various preferred features simplified indicate.The specific design feature of present invention disclosed herein, including, for example,
Specific size, direction, location and shape will partly depend on specific given application and use environment.
In the accompanying drawings, reference numeral refers to the identical or equivalent elements of the present invention in several figures of attached drawing.
Specific implementation mode
It should be understood that terms used herein " vehicle " or " vehicle " or other similar terms include common motor vehicle,
E.g., including sport utility vehicle (SUV), bus, truck, various commercial vehicles car, including various sailer and ships
Water carrier, aircraft etc., and include hybrid electric vehicle, electric vehicle, plug-in hybrid electric vehicles, hydrogen-powered vehicle and its
Its substitute fuel car (for example, fuel of the resource other than oil).As mentioned in this article, hybrid electric vehicle is that have
The vehicle of two or more power sources, for example, having petrol power and electrodynamic vehicle.
Terms used herein are merely to illustrate that specific implementation mode, without being intended to the limitation present invention.As herein
Used, singulative " one, a kind of, should (a, an, the) " is also intended to including plural form, unless in context in addition
Clearly indicate.It is to be further understood that term " including (comprises and/or comprising) " used in the description
Refer to that there are the feature, integer, step, operations, elements, and/or components, but do not preclude the presence or addition of one or more
Other feature, integer, step, operation, component, assembly unit and/or its group.As it is used herein, term "and/or" includes one
Any and all combinations of a or multiple related institutes list.
Unless illustrating or obviously being obtained from context, otherwise the term as used herein " about " is interpreted as in this field
In normal allowable range, such as within the scope of 2 standard deviations of mean value." about " can be understood as the numerical value 10%,
9%, in 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05% or 0.01%.Unless in addition from upper
Hereafter clear from all numerical value provided herein are all modified by term " about ".
Below by each embodiment of the reference present invention in detail, embodiment illustrates in the accompanying drawings, and adds below
With description.Although will be of the invention in conjunction with illustrative embodiments description, it is to be understood that, this specification has no intention office of the present invention
It is limited to these illustrative embodiments.On the contrary, the present invention will not only cover these illustrative embodiments, also to cover by appended
Various alternative forms, modification, equivalents in the spirit and scope of the present invention defined by claim and other embodiment party
Formula.
The present invention can provide the polypropylene resin composites with the physical characteristic significantly improved.By using polypropylene tree
Fat and carbon fiber is used, while will be added to wherein with the modified polypropylene resin that maleic anhydride is grafted, polypropylene tree can be prepared
Fat.
In an exemplary embodiment of the present invention embodiment, allyl resin can be used as homopolymer or the propylene-ethylene copolymerization of propylene
Object and can have be about 20 to about 100g/10min at a temperature of about 230 DEG C melt index (MI) (MI), the molecule of about 5 to about 10
The isotactic index of amount distribution (MWD) and about 97 to about 100.When melt index (MI) is less than predetermined amount, for example, being less than about 20g/
When 10min, molded feature may be caused to be insufficient due to the deterioration of resin flowable；And when melt index (MI) is more than in advance
When quantitative, for example, when greater than about 100g/10min, impact resistance or heat resistance may deteriorate.In addition, when molecular weight distribution is less than
When about 5, machinability may deteriorate；And when molecular weight distribution is greater than about 10, intensity may be decreased.Specifically, Quan Tongli
Structure index can be in the range of about 97 to about 100, to optimize the molded feature and mechanical property of carbon fiber composite.
In an exemplary embodiment of the present invention embodiment, due to the characteristic of acrylic resin as described above, addition has carbon
The bulking agent of fiber can improve compatibility.For example, compared with conventional acrylic resin, not only molded feature but also tensile strength
It can be enhanced with bending strength etc., while other physical characteristics can be enhanced.
In an exemplary embodiment of the present invention embodiment, using about 50wt% to about 80wt%, or it is in particular about 60wt%
To the acrylic resin of the amount of about 70wt%.When polyacrylic amount is more than predetermined amount, it is greater than about 80wt%, various physics
Characteristic may deteriorate；And when its amount is less than predetermined amount, such as less than about 50wt%, molded feature may deteriorate.
In an exemplary embodiment of the present invention embodiment, to improve the compatibility of acrylic resin and carbon fiber etc. together with enhancing
By using the physical characteristic caused by acrylic resin and carbon fiber, the maleic anhydride with 0.5wt% to 15wt% can be connect
The modified polypropene of branch rate is used as bulking agent.When the grafting rate of the maleic anhydride in used modified polypropene is less than predetermined
Amount, such as when less than about 0.5wt%, physical characteristic may cannot improve and the dipping characteristic of compound may deteriorate；When
Grafting rate is more than predetermined amount, for example, when greater than about 15wt%, various physical characteristics may deteriorate.In the exemplary embodiment,
Using about 1wt% to about 10wt%, or it is in particular modified polypropenes of the about 2wt% to the amount of about 7wt%.When its amount is less than pre-
It is quantitative, such as when less than about 1wt%, deterioration in characteristics is impregnated, and work as the modified polypropene used and be significantly greater than predetermined amount, such as
When greater than about 10wt%, it may occur however that physical characteristic deteriorates.
In the exemplary embodiment, carbon fiber is used as reinforcing fiber, to enhance physical characteristic.It can be with about
15wt% is to about 40wt%, or specifically the amount of about 25wt% to about 35wt% includes carbon fiber.When the usage amount of carbon fiber is few
When predetermined amount, such as when less than about 15wt%, mechanical property and heat resistance may deteriorate；And when the carbon fiber used is apparent
More than predetermined amount, for example, when greater than about 40wt%, it may occur however that because mobility deteriorate caused by molded feature deterioration and because of fibre
Dimension amount increases the deterioration of caused dispersibility.
In the exemplary embodiment, one or more additives can be added in polypropylene resin composite.Addition
Agent can conduct, but be not limited to, antioxidant, heat stabilizer, processing aid and UV stabilizer, and can be except component with few
Amount addition.
It can be used as compound according to the polypropylene resin composite of exemplary embodiment of the invention.Specifically, can pass through
It is answered fibre reinforced acrylic resin is prepared in the impregnated carbon fiber to molten mixture of about 15wt% to the amount of about 40wt%
Close object, wherein molten mixture is by the acrylic resin of the amount of about 80wt% and regarding about 50wt% as the pact of bulking agent
The modified polypropene of 1wt% to the amount of about 10wt%, which melts, to be obtained.Therefore, present invention offer is made of polypropylene resin composite
Fibre reinforced acrylic resin compound.
Further it is provided that the method for preparing by using polypropylene resin composite the compound of carbon fiber-containing.
In an exemplary embodiment of the present invention embodiment, polypropylene resin composite can be applied to fibre reinforced polypropylene
Resin complexes.It specifically, as shown in Figure 1, can be exemplary in resin by making composition experience be immersed in reinforcing fiber
It is prepared by process (it may be, but not limited to, normal process steps, such as the molding process for fiber reinforced thermoplastic resin)
Acrylic resin compound.In example procedure, double screw extruder feed resin Composition can be passed through；It then can be from dipping former
The reinforcing fiber of feed such as carbon fiber in tool；And dipping can be executed in resin.It, can be by removing work after completing to impregnate
Sequence (take-off process) prepares compound, but without limitation.In preparation process, such as showing for impregnation mold in fig. 2
Seen in example property internal structure, by sprawling thousands of to tens of thousands of strands of carbon fibers while mobile dipping pin, and make thermoplasticity
Resin is penetrated into fiber stock, can prepare the compound with excellent dispersibility and mechanical property.
In general, the quantity for impregnating pin is more, and the fiber that can be sprawled is more, increases so as to cause dipping characteristic.However,
Cause the fiber of one-ply yarn to be likely to occur breakage because the excessive tensile of fiber is applied to, the same of degree of steeping can be increased
When keep the damage to fiber minimum best pin bank close and may be necessary in preparing thermoplasticity carbon fiber composite.For example,
It is general that about 9 or 10 dipping pins can be used when preparing compound using glass fibre, in the exemplary embodiment party of the present invention
In formula, when specifically selling that dipping characteristic appropriate while reduction is maintained to be applied to the stretching of fiber using about 7 or 8,
Continuous production rate can be enhanced.
In an exemplary embodiment of the present invention embodiment, it is compound that fibre reinforced acrylic resin can be prepared by the following method
Object, this method include：It is about 50wt% to about 80wt% as the poly- of Noblen or propylene-ethylene copolymers to content
Allyl resin adds the modified polypropene as bulking agent that content is about 1wt% to about 10wt%；At about 220 to about 260 DEG C
At a temperature of, by double screw extruder with about 250 to about 400rpm, or specifically about 280 to about 320rpm rotating speed is pinched
Close and melt the mixture of gained；And at about 250 to about 320 DEG C, or specifically in about 260 to about 280 DEG C of impregnation mold
At a temperature of, by the impregnated carbon fiber of about 15wt% to the amount of about 40wt% in molten mixture.Specifically, acrylic resin can
With the melt index (MI) (MI) for being about 20 to about 100g/10min at a temperature of about 230 DEG C, the molecular weight distribution of about 5 to about 10
(MWD) and the isotactic index of about 97 to about 100.In addition, modified polypropene can be with the horse of about 0.5wt% to about 15wt%
Maleic anhydride grafted rate.The compound obtained according to illustrative methods can be thermoplasticity carbon fiber composite.Correspondingly, one is provided
The method that kind is used to prepare fibre reinforced acrylic resin compound.
As described above, each illustrative embodiments according to the present invention, are prepared by using polypropylene resin composite
Fibre reinforced acrylic resin compound, can improve the dipping characteristic of carbon fiber and resin, and can be passed through with low cost
Example procedure prepares the carbon fiber composite of high intensity.In Fig. 3 (a) and (b), pass through 2 He of scanning electron microscopic observation comparative example
The rupture cross section of the exemplary tensile sample of embodiment 2.In Fig. 3 (a), carbon fiber can be clearly observed in conventional composite
Tie up from polypropylene matrix material squeeze out when by hole.In contrast, in Fig. 3 (b), according to the exemplary implementation of the present invention
The compound of mode has a structure in which that is, in this configuration, compound is preferably immersed in PP matrix material
In, while the state that carbon fiber circumference is surrounded by bulking agent being shown.Each embodiment according to the present invention, carbon fiber and poly- third
Interface gravitation (interfacial attraction) maximizing between alkene basis material, and match with existing compound
It sets and compares, can get optimal mechanical characteristic.Specifically, compound according to various exemplary embodiments of the present invention can will be drawn
Intensity enhancing about twice or the tensile strength more than conventional composite are stretched, and can also have the bending strength significantly improved or bullet
Property modulus.
Meanwhile it because can be with each illustrative embodiments according to the present invention as described above by using polypropylene tree
Oil/fat composition prepares the fibre reinforced acrylic resin compound with excellent physical characteristic, so resin combination can
It is applied to the vehicle part with high fluidity and excellent mechanical property.In addition, using by using polypropylene and in addition
With the controlled modified polypropene of molecular structure, improved molded feature is can get, while obtaining improved intensity and springform
Amount.
As described above, compared with conventional resin compositions, when the resin combination of the present invention is applied to various industry productions
When product, there can be required physical characteristic because of improved feature.
In general, when using polypropylene resin composite come when being moulded, can be by adding in extrusion operation
The method of oxide and application cut-out strand, to increase the mobility of resin in some cases.However, this method may
The physical characteristic of raw material resin is set integrally to reduce.Therefore, according to an illustrative embodiment of the invention, by using with height
The polypropylene of mobility and excellent physical characteristic and by increasing molecular weight distribution in the polymerization procedure of monomer, low point
The polypropylene component of son amount can be easily penetrate into carbon fiber bundle, to improve molded feature in moulding part.
In the prior art, carbon fiber generally undergoes sizing treatment by polarity epoxy resin or polyurethane resin
(sizing treatment), when by non-polar polypropylene melting extrusion carbon fiber, it may not be possible to fully show out-of-bounds
Face bonds, insufficient to cause tensile strength or bending strength to increase.However, according to an illustrative embodiment of the invention,
By using PP type bulking agent, intensity can be enhanced via relatively little of carbon fiber content, wherein PP type bulking agent can
The polar group between polarity carbon fiber reinforcement and non-polar polypropylene with predetermined content, to significantly increase affinity
Power.Therefore, the material cost reduced can be obtained by using a small amount of expensive carbon fiber.
As described above, by with particular physical characteristics high fluidity and highly crystalline acrylic resin in make
Be used as a small amount of modified polypropene of bulking agent being grafted through predetermined amount maleic anhydride, carbon fiber can with it is polypropylene resin-based
There is body material the configuration of interface gravitation to impregnate, so as to improve dipping characteristic.Therefore, each illustrative embodiments of the invention
In acrylic resin can have improve intensity and improved mobility.In addition, when impregnation of carbon fibers, acrylic resin can
To be easily penetrate into carbon fiber bundle, to provide the physical characteristic additionally enhanced because of the enhancing of dispersibility.In addition, when according to this
Each illustrative embodiments of invention use the compound in conjunction with polypropylene resin composite, by extrusion forming or are pressed into
Type process and when being molded into various industrial parts, machinability can be improved, circulation time can be reduced, and surface can be significantly increased
Presentation quality.
It can be prepared again by using fibre reinforced polypropylene resin composite with each embodiment according to the present invention
It closes object and industry molding product can be applied to and specifically may be molded and use the component of vehicle.Therefore, it is possible to provide use
The molding product that fibre reinforced polypropylene resin composite is manufactured by being moulded.Specifically, it can manufacture for vehicle
Component.For example, according to an illustrative embodiment of the invention, can manufacture such as damper, buffer, bumper (bumper
Beam), the inside and outside material of front-end module carrier, door impact beam and backrest, pedestal, car body component etc..
Hereinafter, the present invention is described in detail in reference example, but the present invention is not restricted to this.
Embodiment
Following embodiment shows the present invention, but is not intended to limit the present invention.
Embodiment 1
After supplying resin Composition by double screw extruder, the enhancing that such as carbon fiber can be supplied from impregnation mold is fine
Dimension, and dipping is executed in resin.After impregnating, can resin combination be prepared by using process equipment as shown in Figure 1
Object, wherein compound can be prepared by removing process.In this case, about 7 dipping pins can be used in impregnation mold.
It can mix about 67wt%'s by double screw extruder with the rotating speed of about 300rpm at a temperature of about 240 DEG C
The bulking agent -1 of PP-2 (acrylic resin) and about 3wt% is (by Lotte Chemical Corporation manufactures
CM1120H, modified polypropene), carry out melt kneading component used in the preparation of resin combination, and can be at about 270 DEG C
Impregnation mold at a temperature of impregnate the carbon fiber (CF-1, grade name T700SC-24000-50C) of about 30wt%, to obtain
Fibre reinforced polypropylene resin composite, wherein PP-2 have about 15 melt index (MI), about 4 molecular weight distribution and about 96.4
Isotactic index, and bulking agent -1 have about 1% grafting rate.
Embodiment 2 to 4
Can by being prepared in the same manner as example 1, and mixing each independently be respectively provided with about 5%,
The bulking agent -2 of the about 3wt% of about 9% and about 11% grafting rate is (by Lotte Chemical Corporation manufactures
PH200), bulking agent -3 (by the 0555A of Mitsui Chemical Hi-Wax manufactures) and bulking agent -4 are (by Lotte
The GenPoly GMP7550N of Chemical Corporation manufactures), to obtain fibre reinforced polypropylene resin composite.
Embodiment 5 to 6
It can be by being prepared in the same manner as example 1, and the PP-2 of about 65wt% is used, and respectively solely
The bulking agent -1 and bulking agent -2 on the spot mixing about 5wt%, to obtain fibre reinforced propylene resin composition.
Comparative example 1
It can be by being prepared in the same manner as example 1, and the use of melt index (MI) is about 60, molecular weight distribution
It is about 7 and the PP-1 of about 70wt% that isotactic index is about 98.8 is without the use of bulking agent, it is poly- to obtain fibre reinforced
Propylene resin composition.
Comparative example 2
It can be by being prepared in the same manner as example 1, and use the PP-2 of about 70wt% without the use of increasing
Hold agent, to obtain fibre reinforced polypropylene resin composite.
Comparative example 3 and 4
Using the PP-2 of about 70wt%, and can each independently it be made by being prepared in the same manner as example 1
With about 30wt% by Toray Industries, carbon fiber (CF-2, the grade name T700SC-24000- of Inc. manufactures
60E) and by Toray Industries, carbon fiber (CF-3, grade name T700SC-24000-F0E) conduct of Inc. manufactures
Carbon fiber is without the use of bulking agent, to obtain fibre reinforced polypropylene resin composite.
[table 1]
Experimental example 1
In each of embodiment 1 to 6 and comparative example 1 to 4, tensile strength, bending strength, bending modulus and spiral are measured
Stream, and result is shown in table 2.
[table 2]
2 experimental method of table is as follows.
* 1) tensile strength：Standard ASTM D638
* 2) bending strength and bending modulus：Standard ASTM D790
* 3) spiral flow：3123 (injection pressure 100kg/cm of standard ASTM D2, 250 DEG C of injection temperature, spiral mould is wide
Spend 3mm)
As a result, can have the physical characteristic of enhancing, tensile strength according to the embodiment of exemplary embodiment of the invention
With bending strength be comparative example approximately twice as or it is bigger than comparative example.
Experimental example 2
In order to confirm the structure feature of prepared polypropylene resin composite in embodiment 2 and comparative example 2, by sweeping
The rupture cross section of Electronic Speculum (SEM) capture comparative example 2 and the tensile sample of embodiment 2 is retouched, and comparison picture is shown in FIG. 3.
As compared in Fig. 3 picture as a result, the embodiment 2 in Fig. 3 (b) shows such structure, wherein carbon fiber week
Boundary is surrounded by bulking agent and carbon fiber is preferably immersed in PP matrix material, and in the comparative example of Fig. 3 (a) 2
In, it may be clearly seen that when carbon fiber is squeezed out from PP matrix material by hole.
The present invention is described in detail by reference to the preferred embodiment of the present invention.However, those skilled in the art can
Understand, these embodiments can be made a change without departing from the principle and spirit of the invention, model of the invention
It encloses and is limited by the attached claims and its equivalent way.
Claims (8)
1. a kind of polypropylene resin composite, the gross weight based on the polypropylene resin composite include：
Content is 50wt% to 80wt% as Noblen or the acrylic resin of propylene-ethylene copolymers；
Content is the modified polypropene as bulking agent of 1wt% to 10wt%；And
Content is the carbon fiber of 15wt% to 40wt%；
The melt index (MI) that it is 20g/10min to 100g/10min that the wherein described acrylic resin, which has at a temperature of 230 DEG C,
(MI), 5 to 10 molecular weight distribution (MWD) and 97 to 100 isotactic index, and
The wherein described modified polypropene has the maleic anhydride grafting ratio of 5wt% to 11wt%.
2. polypropylene resin composite according to claim 1, wherein the polypropylene resin composite is based on described gather
The gross weight of propylene resin composition include content be the acrylic resin of 60wt% to 70wt%, content is 2wt% to 7wt%'s
Modified polypropene and the carbon fiber that content is 25wt% to 35wt%.
3. a kind of fibre reinforced acrylic resin compound, by the way that the impregnated carbon fiber of the amount of 15wt% to 40wt% exists
It is prepared in molten mixture, the molten mixture includes that content is used as Noblen or third for 50wt% to 80wt%
The acrylic resin and content of alkene-ethylene copolymer are the modified polypropene as bulking agent of 1wt% to 10wt%,
The melt index (MI) that it is 20g/10min to 100g/10min that the wherein described acrylic resin, which has at a temperature of 230 DEG C,
(MI), 5 to 10 molecular weight distribution (MWD) and 97 to 100 isotactic index, and
The wherein described modified polypropene has the maleic anhydride grafting ratio of 5wt% to 11wt%.
4. a kind of method being used to prepare fibre reinforced acrylic resin compound, including：
It it is containing as the addition of the acrylic resin of Noblen or propylene-ethylene copolymers for 50wt% to 80wt% to content
Amount is the modified polypropene as bulking agent of 1wt% to 10wt%；
It is mixed as obtained by rotating speed kneading and melting of the double screw extruder at a temperature of 220 to 260 DEG C with 250 to 400rpm
Close object；And
It is at a temperature of 250 to 320 DEG C of impregnation mold that the impregnated carbon fiber of the amount of 15wt% to 40wt% is mixed in the melting
It closes in object,
The melt index (MI) that it is 20g/10min to 100g/10min that the wherein described acrylic resin, which has at a temperature of 230 DEG C,
(MI), 5 to 10 molecular weight distribution (MWD) and 97 to 100 isotactic index, and
The wherein described modified polypropene has the maleic anhydride grafting ratio of 5wt% to 11wt%.
5. according to the method described in claim 4, wherein in the dipping, sold using 7 or 8 dippings.
6. a kind of molding product, using polypropylene resin composite described in claim 1 by include the steps that molding by
It obtains.
7. molding product according to claim 6, wherein the molding product is the component for vehicle.
8. molding product according to claim 7, wherein the molding product is vehicle bumper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2013-0157328 | 2013-12-17 | ||
| KR1020130157328A KR101526742B1 (en) | 2013-12-17 | 2013-12-17 | A resin composition of carbon fiber reinforced polypropylene with excellent molding property |
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| CN104710687A CN104710687A (en) | 2015-06-17 |
| CN104710687B true CN104710687B (en) | 2018-08-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260389A (en) * | 2010-05-25 | 2011-11-30 | 上海晋飞复合材料科技有限公司 | Method and apparatus for preparing long fiber reinforced thermoplastic resin composite material |
| WO2012143023A1 (en) * | 2011-04-21 | 2012-10-26 | Borealis Ag | Polypropylene homopolymers with high heat deflection temperature, high stiffness and flowability |
| CN103073789A (en) * | 2012-12-24 | 2013-05-01 | 安徽科聚新材料有限公司 | Modified PP (polypropylene) material with long carbon fiber and reinforced conductivity and preparation method thereof |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260389A (en) * | 2010-05-25 | 2011-11-30 | 上海晋飞复合材料科技有限公司 | Method and apparatus for preparing long fiber reinforced thermoplastic resin composite material |
| WO2012143023A1 (en) * | 2011-04-21 | 2012-10-26 | Borealis Ag | Polypropylene homopolymers with high heat deflection temperature, high stiffness and flowability |
| CN103073789A (en) * | 2012-12-24 | 2013-05-01 | 安徽科聚新材料有限公司 | Modified PP (polypropylene) material with long carbon fiber and reinforced conductivity and preparation method thereof |
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