CN103571036A - Recovered carbon fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Recovered carbon fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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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- 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
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- 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
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- 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
- B29C2948/92885—Screw or gear
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention relates to a recovered carbon fiber reinforced polypropylene composite material and a preparation method thereof. The preparation method comprises the following steps: (1) according to a ratio, weighing 5-40 parts of recovered carbon fibers, adding the recovered carbon fibers into a high-speed mixing machine, and adding 0.1-3 parts of a surfactant for performing surface treatment on the recovered carbon fibers; (2) according to the ratio, weighing 60-95 parts of polypropylene, 3-20 parts of a compatilizer, 0-20 parts of a flexibilizer, 0.1-0.6 part of a lubricant, 0.1-0.5 part of an antioxidant and 0-20 parts of fillers, and uniformly mixing in the high-speed mixing machine; (3) adding the uniformly mixed raw materials into a double-screw machine for melting and mixing, extruding, carrying out water cooling, bracing, and dicing to obtain the recovered carbon fiber reinforced PP (polypropylene) composite material. Compared with the prior art, the composite material has the advantages of high strength, excellent mechanical performance, low cost and the like.
Description
Technical field
The invention belongs to macromolecular material recovery technology field, be specifically related to a kind of recovery carbon fiber reinforced polypropylene compound material and preparation method thereof.
Background technology
Carbon-fibre composite (CFRP) has the excellent performance such as light weight, high strength, high-modulus, be that other glass fibre reinforced composions are incomparable, be therefore widely used in the new high-tech industry fields such as aerospace, automotive industry, track traffic, new forms of energy, sports goods.Along with rapid development of economy, CFRP is at the usage quantity rapid growth of every field, and the waste resin producing also grows with each passing day, and composition in discarded CFRP non-degradable all, if be directly discarded in environment, can bring serious pollution to environment on the one hand; On the other hand, in these discarded CFRP, often contain high added value carbon fiber, and the production of carbon fiber is the process of a highly energy-consuming, if do not recycled also, will not cause the serious waste of resource.
Polypropylene (PP) is as a kind of general-purpose plastics, and due to it, to have density low, and mechanical property and processing characteristics are excellent, and the advantage such as low price, has been widely used in automobile, household electrical appliances, the fields such as electrical equipment.And pure PP resin is due to its intensity, hardness, often there are a little deficiencies in the performances such as dimensional stability and thermotolerance, need to can be applied to above-mentioned field to its modification.In order to improve these performances of PP, conventional method is that talcum powder etc. carry out filled modified polypropylene, as described in patent CN1125127 by adopting glass-reinforced polypropylene or adopting mineral filler as calcium carbonate at present.And glass fibre or mineral filler density are larger, the composition density obtaining after filling-modified PP also significantly increases thereupon, this can cause the competitiveness of product in market to decline, simultaneously, be subject to the own performance limitations of glass fibre or mineral filler, adopt the PP performance of glass or mineral filler enhancing modified limited, in the higher applications of some performance requriementss by restricted.In order further to improve the performance of MODIFIED PP matrix material, and make material modified lightweight, make it meet the application to the higher field of performance requriements, a kind of method is to adopt carbon fiber enhancing modified PP, as described in patent CN100368471, CN100478386, the matrix material preparing not only intensity is high, excellent performance, and also density is low; But new carbon fiber is expensive, this has also caused the PP matrix material cost that obtains by its enhancing modified higher, and this has directly limited it and has been widely used.
Summary of the invention
Object of the present invention is exactly to provide recovery carbon fiber reinforced polypropylene compound material that a kind of intensity is high, mechanical property is excellent, cost is low and preparation method thereof in order to overcome the defect of above-mentioned prior art existence.
Object of the present invention can be achieved through the following technical solutions: a kind of recovery carbon fiber reinforced polypropylene compound material, it is characterized in that, and the component that said composition comprises following weight part is made:
Described polypropylene is homo-polypropylene or Co-polypropylene.
Described recovery carbon fiber is to reclaim gained from discarded CFRP, and carbon fiber length is 0.1mm-100mm.
Described surface treatment agent is one or more in silane coupling agent, titanate coupling agent and aluminate coupling agent.
Described compatilizer is one or more in maleic anhydride inoculated polypropylene (PP-g-MAH), acrylic acid-grafted polypropylene (PP-g-AA) and ethylene-methyl acrylate-glyceryl methacrylate random terpolymer (AX8900).
Described toughner is one or more in ethylene-octene copolymer (POE), terpolymer EP rubber (EPDM), styrene-butadiene rubber(SBR) (SBS), ethylene-propylene rubber(EPR) (EPR).
Described lubricant is one or more in stearic acid, calcium stearate, Zinic stearas, Ployethylene Wax, white oil; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, oxidation inhibitor 1098, irgasfos 168.
Described filler is the mineral fillers such as calcium carbonate, talcum powder, mica, polynite, and preferable particle size is 800-3000 order.
A preparation method who reclaims carbon fiber reinforced polypropylene compound material, is characterized in that, comprises the following steps:
(1) by said ratio, the recovery carbon fiber that takes 5-40 part joins in high mixer, then adds the surface treatment agent of 0.1-3 part to carry out surface treatment to reclaiming carbon fiber;
(2) by proportioning, take 60-95 part polypropylene again, 3-20 part compatilizer, 0-20 part toughner, 0.1-0.6 part lubricant, 0.1-0.5 part oxidation inhibitor, 0-20 part filler, in high mixer, mixes;
(3) raw material step (2) being mixed joins melt blending in dual-screw-stem machine, extrudes, and water-cooled, tie rod pelletizing is recycled carbon fiber reinforced PP composition.
The twin screw extruder of described step (3) is in the same way or counter rotation twin screw extruder, and extruder temperature is 180-230 ℃, and screw speed is 150-400rpm, and screw slenderness ratio L/D is 30-50:1.
One of object of the present invention is to provide a kind of recovery carbon fiber reinforced polypropylene compound material, and this matrix material not only has that intensity is high, mechanical property is excellent, low cost and other advantages; This composite material by adopting is that the carbon fiber reclaiming from discarded CFRP material carries out enhancing modified to matrix resin simultaneously, and discarded carbon fiber is re-used, and has reduced its pollution to environment, has increased its added value, has saved resource.
Another object of the present invention is to provide a kind of preparation method of above-mentioned recovery carbon fiber reinforced polypropylene compound material, and this preparation method's process operation is simple.
Compared with prior art, recovery carbon fiber reinforced polypropylene compound material provided by the present invention not only has that intensity is high, mechanical property is excellent, low cost and other advantages; What the more important thing is this composite material by adopting is that the carbon fiber reclaiming from discarded CFRP material carries out enhancing modified to matrix resin, and discarded carbon fiber is re-used, and has reduced its pollution to environment, has increased its added value, has saved resource.The matrix material preparing can be widely used in aerospace, automobile, machinery, electronic apparatus, the product components such as household electrical appliances.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
In following examples, tensile property testing standard is ASTM D638, and bending property testing standard is ASTMD790, and Izod notched Izod impact strength testing standard is ASTM D256.
Embodiment 1
(1) take 10 parts and reclaim carbon fiber in high mixer, carbon fiber length is 0.1mm, adds 0.1 part of silane coupling agent KH560 surface treatment to reclaim carbon fiber.
(2) take 90 parts of homo-polypropylene, 3 parts of PP-g-MAH, 0.1 part of stearic acid, 0.3 part of anti-1010,0.1 parts of anti-168,20 part of 800 order calcium carbonate is even in high-speed mixer and mixing.
(3) raw material mixing is added in twin screw extruder, melt blending, extrudes, tie rod pelletizing obtains required recovery carbon fiber and strengthens PP matrix material, and each district's temperature of twin screw extruder is: 195 ℃, 185 ℃， 2nd district, a district, three 215 ℃, 205 205 ℃， 5th district, ℃， 4th district, districts, six 215 ℃, districts, seven 230 ℃, 225 225 ℃， 9th district, ℃， 8th district, districts, ten 230 ℃, districts, 225 ℃ of heads; Screw speed 400rpm, length-to-diameter ratio L/D=30/1.
Embodiment 2
(1) take 20 parts and reclaim carbon fiber in high mixer, carbon fiber length is 1mm, adds 0.4 part of Silane coupling agent KH550 surface treatment to reclaim carbon fiber.
(2) take 80 parts of Co-polypropylene, 10 parts of AX8900,10 parts of POE, 0.3 part of Zinic stearas, 0.2 part of anti-1076,0.2 parts of anti-168,5 part of 2500 order talcum powder is even in high-speed mixer and mixing.
(3) raw material mixing is added in twin screw extruder, melt blending, extrudes, tie rod pelletizing obtains required recovery carbon fiber and strengthens PP matrix material, and each district's temperature of twin screw extruder is: 195 ℃, 185 ℃， 2nd district, a district, three 215 ℃, 205 205 ℃， 5th district, ℃， 4th district, districts, six 215 ℃, districts, seven 230 ℃, 225 225 ℃， 9th district, ℃， 8th district, districts, ten 230 ℃, districts, 225 ℃ of heads; Screw speed 250rpm, length-to-diameter ratio L/D=40/1.
Embodiment 3
(1) take 30 parts and reclaim carbon fiber in high mixer, carbon fiber length is 10mm, adds the 3 parts of different stearoyl titanic acid ester of titanate coupling agent sec.-propyl three surface treatments to reclaim carbon fiber.
(2) take 70 parts of Co-polypropylene, 15 parts of PP-g-MAA, 20 parts of EPDM, 0.6 part of Ployethylene Wax, 0.2 part anti-1098,0.2 parts anti-168 even in high-speed mixer and mixing.
(3) raw material mixing is added in twin screw extruder, melt blending, extrudes, tie rod pelletizing obtains required recovery carbon fiber and strengthens PP matrix material, and each district's temperature of twin screw extruder is: 195 ℃, 185 ℃， 2nd district, a district, three 215 ℃, 205 205 ℃， 5th district, ℃， 4th district, districts, six 215 ℃, districts, seven 230 ℃, 225 225 ℃， 9th district, ℃， 8th district, districts, ten 230 ℃, districts, 225 ℃ of heads; Screw speed 350rpm, length-to-diameter ratio L/D=50/1.
Embodiment 4
(1) take 5 parts and reclaim carbon fiber in high mixer, carbon fiber length is 100mm, adds 2 parts of titanate coupling agent sec.-propyls three (dodecyl benzenesulfonyl) titanic acid ester surface treatment to reclaim carbon fiber.
(2) take 95 parts of Co-polypropylene, 5 parts of PP-g-MAH, 3 parts of SBS, 0.5 part of white oil, 0.3 part of anti-1010,0.1 parts of anti-168,15 part of 1250 order polynite is even in high-speed mixer and mixing.
(4) raw material mixing is added in twin screw extruder, melt blending, extrudes, tie rod pelletizing obtains required carbon fiber and strengthens PP matrix material, and each district's temperature of twin screw extruder is: 195 ℃, 185 ℃， 2nd district, a district, three 215 ℃, 205 205 ℃， 5th district, ℃， 4th district, districts, six 215 ℃, districts, seven 230 ℃, 225 225 ℃， 9th district, ℃， 8th district, districts, ten 230 ℃, districts, 225 ℃ of heads; Screw speed 150rpm, length-to-diameter ratio L/D=40/1.
Embodiment 5
(1) take 20 parts and reclaim carbon fiber in high mixer, carbon fiber length is 6mm, adds 2 parts of aluminate coupling agent distearyl acyl-oxygen sec.-propyl Aluminate surface treatments to reclaim carbon fiber.
(3) take 80 parts of homo-polypropylene, 15 parts of PP-g-MAH, 5 parts of EPR, 0.5 part of calcium stearate, 0.3 part of anti-1010,0.1 parts of anti-168,5 part of 1250 order mica is even in high-speed mixer and mixing.
(4) raw material mixing is added in twin screw extruder, melt blending, extrudes, tie rod pelletizing obtains required recovery carbon fiber and strengthens PP matrix material, and each district's temperature of twin screw extruder is: 195 ℃, 185 ℃， 2nd district, a district, three 215 ℃, 205 205 ℃， 5th district, ℃， 4th district, districts, six 215 ℃, districts, seven 230 ℃, 225 225 ℃， 9th district, ℃， 8th district, districts, ten 230 ℃, districts, 225 ℃ of heads; Screw speed 300rpm, length-to-diameter ratio L/D=40/1.
Each embodiment mechanical experimental results is as shown in table 1 below:
Table 1 mechanical experimental results
From upper table, mechanical experimental results is analyzed, and adopts recovery carbon fiber reinforced PP composite material strength high, and mechanical property is excellent, meets the higher occasion of performance requriements is used.
Embodiment 6
(1) take 40 parts and reclaim carbon fiber in high mixer, carbon fiber length is 100mm, adds 3 parts of aluminate coupling agent distearyl acyl-oxygen sec.-propyl Aluminate surface treatments to reclaim carbon fiber.
(3) take 60 parts of homo-polypropylene, 20 parts of PP-g-MAH, 15 parts of EPR, 0.5 part of calcium stearate, 0.1 part of anti-168,10 part of 1250 order polynite is even in high-speed mixer and mixing.
(4) raw material mixing is added in twin screw extruder, melt blending, extrudes, tie rod pelletizing obtains required recovery carbon fiber and strengthens PP matrix material, and each district's temperature of twin screw extruder is: 195 ℃, 185 ℃， 2nd district, a district, three 215 ℃, 205 205 ℃， 5th district, ℃， 4th district, districts, six 215 ℃, districts, seven 230 ℃, 225 225 ℃， 9th district, ℃， 8th district, districts, ten 230 ℃, districts, 225 ℃ of heads; Screw speed 150rpm, length-to-diameter ratio L/D=40/1.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to embodiment, and the General Principle of this explanation is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. reclaim a carbon fiber reinforced polypropylene compound material, it is characterized in that, the component that said composition comprises following weight part is made:
2. recovery carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, described polypropylene is homo-polypropylene or Co-polypropylene.
3. recovery carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, described recovery carbon fiber is to reclaim gained from discarded CFRP, and carbon fiber length is 0.1mm-100mm.
4. recovery carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, described surface treatment agent is one or more in silane coupling agent, titanate coupling agent and aluminate coupling agent.
5. recovery carbon fiber reinforced polypropylene compound material according to claim 1, it is characterized in that, described compatilizer is one or more in maleic anhydride inoculated polypropylene (PP-g-MAH), acrylic acid-grafted polypropylene (PP-g-AA) and ethylene-methyl acrylate-glyceryl methacrylate random terpolymer (AX8900).
6. recovery carbon fiber reinforced polypropylene compound material according to claim 1, it is characterized in that, described toughner is one or more in ethylene-octene copolymer (POE), terpolymer EP rubber (EPDM), styrene-butadiene rubber(SBR) (SBS), ethylene-propylene rubber(EPR) (EPR).
7. recovery carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, described lubricant is one or more in stearic acid, calcium stearate, Zinic stearas, Ployethylene Wax, white oil; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, oxidation inhibitor 1098, irgasfos 168.
8. recovery carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, described filler is the mineral fillers such as calcium carbonate, talcum powder, mica, polynite, and preferable particle size is 800-3000 order.
9. a preparation method for recovery carbon fiber reinforced polypropylene compound material as claimed in claim 1, is characterized in that, comprises the following steps:
(1) by said ratio, the recovery carbon fiber that takes 5-40 part joins in high mixer, then adds the surface treatment agent of 0.1-3 part to carry out surface treatment to reclaiming carbon fiber;
(2) by proportioning, take 60-95 part polypropylene again, 3-20 part compatilizer, 0-20 part toughner, 0.1-0.6 part lubricant, 0.1-0.5 part oxidation inhibitor, 0-20 part filler, in high mixer, mixes;
(3) raw material step (2) being mixed joins melt blending in dual-screw-stem machine, extrudes, and water-cooled, tie rod pelletizing is recycled carbon fiber reinforced PP composition.
10. the preparation method of recovery carbon fiber reinforced polypropylene compound material according to claim 9, it is characterized in that, the twin screw extruder of described step (3) is in the same way or counter rotation twin screw extruder, extruder temperature is 180-230 ℃, screw speed is 150-400rpm, and screw slenderness ratio L/D is 30-50:1.
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| CN105199234A (en) * | 2015-11-11 | 2015-12-30 | 贵州凯科特材料有限公司 | Carbon fiber reinforced polypropylene composite and preparation method thereof |
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| CN108690259A (en) * | 2017-04-10 | 2018-10-23 | 广州金发碳纤维新材料发展有限公司 | A kind of fibre reinforced PP composite material and preparation method thereof |
| US20190337271A1 (en) * | 2018-05-04 | 2019-11-07 | Ford Global Technologies, Llc | Reinforced polypropylene/micronized tire rubber polymer compatible with structural foam molding process |
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| US20190337271A1 (en) * | 2018-05-04 | 2019-11-07 | Ford Global Technologies, Llc | Reinforced polypropylene/micronized tire rubber polymer compatible with structural foam molding process |
| GB2588922A (en) * | 2019-11-14 | 2021-05-19 | Horizon Int Ltd | A modified polypropylene-based cooling tower filler and its production process |
| GB2588922B (en) * | 2019-11-14 | 2022-12-07 | Horizon Int Ltd | A modified polypropylene-based cooling tower filler and its production process |
| CN110862607A (en) * | 2019-11-25 | 2020-03-06 | 南通复源新材料科技有限公司 | Regenerated carbon fiber reinforced PP (polypropylene) material based on ultrasonic technology and preparation method thereof |
| CN110862608B (en) * | 2019-11-25 | 2022-02-25 | 南通复源新材料科技有限公司 | Regenerated carbon fiber reinforced PP material and preparation method thereof |
| CN110862608A (en) * | 2019-11-25 | 2020-03-06 | 南通复源新材料科技有限公司 | Regenerated carbon fiber reinforced PP material and preparation method thereof |
| CN112029194A (en) * | 2020-08-31 | 2020-12-04 | 山东非金属材料研究所 | Recycled carbon fiber/polypropylene composite material and preparation method thereof |
| CN112898686A (en) * | 2021-02-04 | 2021-06-04 | 广东金毅玩具材料有限公司 | Sprayable polypropylene-polystyrene alloy material and preparation method thereof |
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