CN116622156A - Multi-scale, low-warpage and high-weld-mark-strength long glass fiber reinforced recycled polypropylene composite material and preparation method thereof - Google Patents
Multi-scale, low-warpage and high-weld-mark-strength long glass fiber reinforced recycled polypropylene composite material and preparation method thereof Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 103
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 87
- -1 polypropylene Polymers 0.000 title claims abstract description 87
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 22
- 238000007598 dipping method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 239000012258 stirred mixture Substances 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 10
- 239000005357 flat glass Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004033 plastic Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000009471 action Effects 0.000 description 7
- 238000007605 air drying Methods 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 4
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- 230000000694 effects Effects 0.000 description 3
- 238000003878 thermal aging Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention discloses a long glass fiber reinforced regenerated polypropylene composite material with multiple dimensions, low warpage and high weld mark strength and a preparation method thereof, and the long glass fiber reinforced regenerated polypropylene composite material comprises, by mass, 20% -70% of polypropylene resin, 20% -70% of regenerated polypropylene resin, 20% -50% of continuous long glass fiber, 20% -50% of flat long glass fiber, 2% -5% of compatilizer, 2% -5% of auxiliary agent master batch such as antioxidant and the like. The invention is characterized in that the regenerated polypropylene and the flat glass fiber are introduced into a conventional long glass fiber reinforced polypropylene formula system, and simultaneously are matched with the mixture of different scales, so that the long glass fiber reinforced regenerated polypropylene composite material with multiple scales, low warpage and high weld mark strength can be obtained; compared with the conventional long glass fiber reinforced polypropylene material, the mechanical property of the material is improved, the weld mark strength and appearance are also obviously improved, meanwhile, the warping resistance of the product is better, the homo-polymerization reclaimed material is added, the material performance is ensured, and meanwhile, the requirement of sustainable development is met.
Description
Technical Field
The invention relates to a preparation method of a long glass fiber reinforced regenerated polypropylene composite material. In particular to a preparation method of a long glass fiber reinforced recycled polypropylene composite material with multiple dimensions, low warpage and high weld mark strength.
Background
At present, in the context of global warming and energy shortage, automobile weight reduction is a significant direction of automobile development. Among them, "replace steel with plastic" is the trend of light weight, light weight and excellent price are also one of the reasons why it is widely selected and replaced. The front end module, the tail gate module and the like are prepared by adopting the all-plastic composite material, and the front end module, the tail gate module and the like have the advantages of high design flexibility, light weight, shock resistance, shock absorption and the like, and all large host factories are actively developing research, development, application and verification work at present. The long glass fiber reinforced polypropylene composite material is often selected in the fields of front end modules, tail gate templates and the like of automobiles because of excellent mechanical properties, high heat resistance, good creep resistance, high and low temperature impact resistance and the like. However, the requirements of the front end module and the tail gate module on the rigidity strength, the impact resistance, the dimensional stability and the like of the materials are particularly high, and along with the continuous improvement of the design and integration degree of the structural modules of parts of different types in the market, the materials are also challenged, the requirements of the front end design and the working conditions of the parts are hardly met by common long fiber reinforced polypropylene, and the assembly difficulties such as the warp deformation, the serious post shrinkage, the torque failure and the like of the parts are also caused.
In view of the above, there is still a need to develop a method for preparing a long glass fiber reinforced polypropylene composite material with multi-scale, low warpage and high weld mark strength, which has better rigidity strength, impact resistance and dimensional stability, and meanwhile, the use condition of parts can be better maintained.
Disclosure of Invention
The invention aims at solving the problems commonly existing in the conventional long glass fiber reinforced polypropylene material, and provides a multi-scale customizable long glass fiber composite material solution to meet the market demands; the invention provides a preparation method of a long glass fiber reinforced recycled polypropylene composite material with multiple dimensions, low warpage and high weld mark strength.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the long glass fiber reinforced recycled polypropylene composite material with the advantages of multiple dimensions, low warpage and high weld mark strength comprises the following raw materials in percentage by weight:
20% -70% of polypropylene resin;
20% -70% of regenerated polypropylene resin;
20% -50% of continuous long glass fibers;
20-50% of flat long glass fibers;
2% -5% of a compatilizer;
1% -2% of antioxidant;
0.2% -1% of lubricant;
0.8% -2% of black matrix.
In the case of this formulation system, the components,
the melt index of the polypropylene resin is 30-100g/10min.
The melt index of the regenerated polypropylene resin is 20-60g/10min.
The diameter of the continuous long glass fiber monofilament is 10-30 mu m, and the linear density is 1200, 2400 and 4800. The continuous long glass fiber is coated with a layer of silicone auxiliary agent and polyolefin sizing agent before entering the dipping tank, so that a good interface layer is formed between the glass fiber and the resin.
The ratio of the length to the width of the cross section of the flat long glass fiber is 1:4-1:3, the diameter of a single filament is 10-13 mu m, and the linear density is 1200, 2400 and 4800. The continuous flat long glass fiber is coated with a layer of silicone auxiliary agent and polyolefin sizing agent before entering the dipping tank, so that a good interface layer is formed between the glass fiber and the resin.
The compatilizer is maleic anhydride graft, the grafting rate is 1.2%, and the compatilizer plays a role in compatibilization in a system.
The antioxidant is a compound mixture of main antioxidants and auxiliary antioxidants, wherein the main antioxidants adopt hindered phenol antioxidants, and the auxiliary antioxidants adopt thioesters and phosphite esters.
The lubricant is ethylene bis-stearamide or silicone master batch.
The black master batch is master batch with the particle size of 1-3mm and is composed of inorganic toner filled polypropylene.
The invention also provides a preparation method of the long glass fiber reinforced regenerated polypropylene composite material, which comprises the following steps:
step one: the polypropylene resin, the regenerated polypropylene resin, the compatilizer, the antioxidant, the lubricant and the black matrix are put into a stirrer according to the corresponding mass proportion, and the equipment parameters of the stirrer are set to be 10min, and the rotating speed is 800r/min. Pouring the uniformly stirred mixture into a feed opening of a double-screw extruder, and allowing the material to flow into a dipping tank at a constant conveying speed after shearing, plasticizing and homogenizing of the double screws, wherein the processing temperature of the extruder is 150-250 ℃ and the rotating speed of a host machine is 250-280rpm.
Step two: and (3) introducing the compound obtained by the mixed extrusion in the step (I) into a special dipping die cavity, wherein the processing temperature of the dipping die cavity is 270-285 ℃. And then adopting a pultrusion process to uniformly infiltrate and wrap the surfaces of the long glass fibers and the flat long glass fibers penetrating through the die cavity with polypropylene resin, finally cooling the infiltrated continuous glass fibers through a water tank, drawing, and granulating by a granulator to obtain two types of long glass fiber particles with different lengths.
Step three: and (3) uniformly mixing the two types of particles obtained in the step two according to a certain proportion to obtain the finished long glass fiber reinforced polypropylene composite material.
The processing temperature of the extruder in the first step is 235 ℃, and the rotating speed of a host machine is 270rpm;
setting the temperature of the dipping tank at 280 ℃;
the linear density of the long glass fiber reinforced recycled polypropylene is 2400Tex, and the grain cutting length is 4-6mm,6-8mm and 10-12mm.
The mechanism of the invention is as follows:
according to the invention, the micro-flow of composite components is increased by introducing flat long glass fiber composite materials with different dimensions into the conventional long glass fiber reinforced materials, and the flat glass fiber has better performance in the same state due to the large specific surface area and better impregnation effect; compared with the conventional long glass fiber reinforced polypropylene composite material, the distribution of fiber reinforcement in the product after injection molding is more reasonable, short flat fibers serving as auxiliary reinforcement are uniformly dispersed among long fiber bundles, so that the anisotropy caused by the flow orientation of transverse and longitudinal glass fibers is reduced, the buckling deformation is reduced, and the glass fiber orientation at the weld mark position is improved;
compared with the prior art, the invention has the advantages that: (1) The regenerated polypropylene resin suitable for the system is selected, and compared with the brand new material, the performance and the like are kept consistent; (2) Compared with the conventional long glass fiber reinforced polypropylene material, the introduction of the flat long glass fiber is beneficial to weakening the anisotropy of the glass fiber flow due to the spiral flow of the composite glass fiber component, so that the buckling deformation caused by the uneven shrinkage of the long fiber reinforced material in the transverse and longitudinal directions can be weakened, and meanwhile, the introduction of the flat long glass fiber can provide better weld mark strength for the material due to the position of a weld line. (3) Through formula design optimization, material performance and material price can be selectively screened to match the requirements of the part outline.
The specific embodiment is as follows:
the present invention will be further illustrated by the following examples and comparative examples, and the present invention should not be limited to what is specifically illustrated by the following experimental examples without departing from the spirit of the present invention.
The raw materials used in the examples are as follows:
polypropylene resin: melt index 60g/10min, exxon Mobil
Regenerated homopolymerized polypropylene resin: melt index 20g/10min, green Mei
Continuous long glass fiber: eurasian Kening
Flat long glass fiber: chongqing International
And (3) a compatilizer: maleic anhydride grafted polypropylene, good and easy to market
An antioxidant: 1010; hindered phenolic antioxidant, company CIBA, switzerland
An antioxidant: 619F; thiodipropionic acid distearate; commercially available
An antioxidant: DSTP; phosphite antioxidants; commercially available
And (3) a lubricant: silicone master batches, commercially available
Black matrix: e320, commercially available
Example 1
58kg of polypropylene resin, 6kg of regenerated polypropylene resin, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is put into a feed opening of a double-screw extruder after being uniformly mixed, materials are finally conveyed into an impregnating tank through a conveying section, a compressing section and an extruding section, meanwhile, continuous long glass fibers enter the impregnating tank through a yarn guide roller and a die cavity under the action of traction equipment, pass out from the other end of the impregnating tank at a constant moving speed, melt is solidified after meeting cold water, and the long glass fiber reinforced regenerated polypropylene composite material can be obtained after air drying, the length of plastic particles is 10mm-12mm, and the glass fiber content is controlled to be 30%.
Example 2
51kg of polypropylene resin, 13kg of regenerated polypropylene resin, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is put into a feed opening of a double-screw extruder after being uniformly mixed, materials are finally conveyed into an impregnating tank through a conveying section, a compressing section and an extruding section, meanwhile, continuous long glass fibers enter the impregnating tank through a yarn guide roller and a die cavity under the action of traction equipment, pass out from the other end of the impregnating tank at a constant moving speed, melt is solidified after meeting cold water, and the long glass fiber reinforced regenerated polypropylene composite material can be obtained after air drying, the length of plastic particles is 10mm-12mm, and the glass fiber content is controlled to be 30%.
Example 3
44kg of polypropylene resin, 20kg of regenerated polypropylene resin, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is put into a feed opening of a double-screw extruder after being uniformly mixed, materials are finally conveyed into an impregnating tank through a conveying section, a compressing section and an extruding section, meanwhile, continuous long glass fibers enter the impregnating tank through a yarn guide roller and a die cavity under the action of traction equipment, pass out from the other end of the impregnating tank at a constant moving speed, melt is solidified after meeting cold water, and the long glass fiber reinforced regenerated polypropylene composite material can be obtained after air drying, the length of plastic particles is 10mm-12mm, and the glass fiber content is controlled to be 30%.
Example 4
The long glass fiber reinforced polypropylene particles obtained in example 1 and comparative example 2 were blended in a mass ratio of 1:1 to obtain a long glass fiber reinforced recycled polypropylene material example 4.
Example 5
The long glass fiber reinforced polypropylene particles obtained in example 1 and comparative example 2 were blended in a mass ratio of 1:2 to obtain a long glass fiber reinforced recycled polypropylene material example 5.
Example 6
The long glass fiber reinforced polypropylene particles obtained in example 1 and comparative example 2 were blended in a mass ratio of 2:1 to obtain a long glass fiber reinforced recycled polypropylene material example 6.
Example 7
The long glass fiber reinforced polypropylene particles obtained in example 1 and comparative example 3 were blended in a mass ratio of 1:2 to obtain a long glass fiber reinforced recycled polypropylene material example 7.
Example 8
The long glass fiber reinforced polypropylene particles obtained in example 1 and comparative example 4 were blended in a mass ratio of 1:2 to obtain a long glass fiber reinforced recycled polypropylene material example 8.
Comparative example 1
64kg of polypropylene resin, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is put into a feed opening of a double-screw extruder after being uniformly mixed, the materials are finally conveyed into an impregnating tank through a conveying section, a compressing section and an extruding section, meanwhile, continuous long glass fibers enter the impregnating tank through a yarn guide roller and a die cavity under the action of traction equipment, pass out from the other end of the impregnating tank at a constant moving speed, melt is solidified after encountering cold water, and the long glass fiber reinforced polypropylene composite material can be obtained after air drying and granulating and drying, the length of plastic particles is 10mm-12mm, and the glass fiber content is controlled to be 30%.
Comparative example 2
64kg of polypropylene resin, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is put into a feed opening of a double-screw extruder after being uniformly mixed, the materials are finally conveyed into an impregnating tank through a conveying section, a compressing section and an extruding section, meanwhile, flat long glass fibers enter the impregnating tank through a yarn guide roller and a die cavity under the action of traction equipment, pass out from the other end of the impregnating tank at a constant moving speed, melt is solidified after encountering cold water, and the long glass fiber reinforced polypropylene composite material can be obtained after air drying and granulating and drying, the length of plastic particles is 10mm-12mm, and the glass fiber content is controlled to be 30%.
Comparative example 3
64kg of polypropylene resin, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is put into a feed opening of a double-screw extruder after being uniformly mixed, the materials are finally conveyed into an impregnating tank through a conveying section, a compressing section and an extruding section, meanwhile, flat long glass fibers enter the impregnating tank through a yarn guide roller and a die cavity under the action of traction equipment, pass out from the other end of the impregnating tank at a constant moving speed, melt is solidified after encountering cold water, and the long glass fiber reinforced polypropylene composite material can be obtained after air drying and granulating and drying, the length of plastic particles is 4mm-6mm, and the glass fiber content is controlled to be 30%.
Comparative example 4
64kg of polypropylene resin, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is put into a feed opening of a double-screw extruder after being uniformly mixed, the materials are finally conveyed into an impregnating tank through a conveying section, a compressing section and an extruding section, meanwhile, flat long glass fibers enter the impregnating tank through a yarn guide roller and a die cavity under the action of traction equipment, pass out from the other end of the impregnating tank at a constant moving speed, melt is solidified after encountering cold water, and the long glass fiber reinforced polypropylene composite material can be obtained after air drying and granulating and drying, the length of plastic particles is 6mm-8mm, and the glass fiber content is controlled to be 30%.
The particles prepared in the above examples and comparative examples were subjected to material-level and part-level performance tests, test items and test methods as follows:
tensile properties: the stretching speed was 5mm/min according to ISO 527-2.
Bending properties: the test speed was 2mm/min according to ISO 178.
Notched impact strength: testing according to ISO 179-1 at normal temperature of 23 deg.C and-40 deg.C respectively.
Weld mark strength: the weld mark mold was subjected to stretching to test for stretching properties according to ISO 527-2.
Torsional stiffness test: the front end module is prepared by adopting the particle proofing method, one side of the plastic front end module frame is fixed at the temperature of 23 ℃, and the other side rotates along the central axis by +/-9 degrees.
Insert torsional force test: the torsional resistance of the insert was measured with a torsional moment at 23 ℃ ± 2, and if the front end module was damaged at not less than 11 n.m.
Thermal aging test: the sample should be placed in an oven at 120 ℃ for 168 hours (7 days), then the product state is evaluated after being placed for 1 hour at normal temperature, and the deformation amount is tested by adopting three coordinates.
Apparent mass: according to visual appearance judgment, marking agglomeration points with the surface of more than or equal to 3mm on a 10-die observation surface; more than or equal to 3 are regarded as agglomeration;
the properties of the long glass fiber reinforced polypropylene materials for front end modules obtained in the above examples and comparative examples are shown in Table 1 and Table 2
TABLE 1
By comparing the test data of comparative examples and examples in Table 1, it can be obtained that the tensile property and bending property of the material have less influence along with the improvement of the content of the regenerated homopolypropylene on the premise that the content of the long glass fiber is kept to be 30%; when 30% recycled polypropylene was added; the impact performance is reduced by about 23 percent; the addition of the reclaimed materials has no improvement effect on torsional rigidity and weld mark strength; the appearance and the thermal aging deformation rate are improved.
TABLE 2
By comparing test data of comparative examples and examples in Table 2, it can be obtained that the material performance is improved by 10-15% by introducing flat glass fiber into the system, and the weld mark strength, torque rigidity and deformation rate are increased along with the increase of the content of the flat glass fiber; when 30% recycled polypropylene was added; the impact performance is reduced by about 23 percent; the addition of the reclaimed materials has no improvement effect on torsional rigidity and weld mark strength; the appearance and the thermal aging deformation rate are improved;
TABLE 3 Table 3
By comparing test data of comparative examples and examples in Table 3, it can be obtained that the material performance is comprehensively improved by introducing 4-6mm and 6-8mm flat glass fiber reinforced polypropylene particles into the system, wherein the improvement of weld mark strength is maximum and is improved by 51% when 6-8mm particles are introduced;
compared with the conventional long glass fiber reinforced polypropylene material, the special scheme of the long glass fiber reinforced polypropylene material with low warpage and high weld mark strength has the advantages of improving the mechanical property, the dimensional stability and the like, and simultaneously having the characteristics of low warpage and high weld mark strength; as a composite material with excellent comprehensive performance and high cost performance, the composite material can be well applied to the field of automobile light weight.
Claims (10)
1. A long glass fiber reinforced recycled polypropylene composite material with multiple dimensions, low warpage and high weld mark strength is characterized in that: the material is prepared from the following raw materials in percentage by weight:
20% -70% of polypropylene resin;
20% -70% of regenerated polypropylene resin;
20% -50% of continuous long glass fibers;
20-50% of flat long glass fibers;
2% -5% of a compatilizer;
1% -2% of antioxidant;
0.2% -1% of lubricant;
0.8% -2% of black matrix.
2. The multi-scale, low warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material of claim 1, wherein: the melt index of the polypropylene resin is 30-100g/10min.
3. The multi-scale, low warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material of claim 1, wherein: the melt index of the regenerated polypropylene resin is 20-60g/10min.
4. The multi-scale, low warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material of claim 1, wherein: the diameter of the continuous long glass fiber monofilament is 10-30 mu m, and the linear density is 1200, 2400 and 4800. The continuous long glass fiber is coated with a layer of silicone auxiliary agent and polyolefin sizing agent before entering the dipping tank, so that a good interface layer is formed between the glass fiber and the resin.
5. The multi-scale, low warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material of claim 1, wherein: the ratio of the length to the width of the cross section of the flat long glass fiber is 1:4-1:3, the diameter of a single filament is 10-13 mu m, and the linear density is 1200, 2400 and 4800. The continuous flat long glass fiber is coated with a layer of silicone auxiliary agent and polyolefin sizing agent before entering the dipping tank, so that a good interface layer is formed between the glass fiber and the resin.
6. The multi-scale, low warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material of claim 1, wherein: the compatilizer is maleic anhydride graft, and the grafting rate is 1.2%.
7. The multi-scale, low warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material of claim 1, wherein: the antioxidant is a compound mixture of main antioxidants and auxiliary antioxidants, wherein the main antioxidants adopt hindered phenol antioxidants, and the auxiliary antioxidants adopt thioesters and phosphite esters;
the lubricant is ethylene bis-stearamide or silicone master batch.
8. The multi-scale, low warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material of claim 1, wherein: the black master batch is master batch with the particle size of 1-3mm and is composed of inorganic toner filled polypropylene.
9. The method for preparing the multi-scale, low-warpage and high weld mark strength long glass fiber reinforced recycled polypropylene composite material according to any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
step one: the polypropylene resin, the regenerated polypropylene resin, the compatilizer, the antioxidant, the lubricant and the black matrix are put into a stirrer according to the corresponding mass proportion, the equipment parameters of the stirrer are set to be 10min, and the rotating speed is 800r/min; pouring the uniformly stirred mixture into a feed opening of a double-screw extruder, and allowing the material to flow into a dipping tank at a constant conveying speed after shearing, plasticizing and homogenizing of the double screws, wherein the processing temperature of the extruder is 150-250 ℃ and the rotating speed of a host machine is 250-280rpm;
step two: and (3) introducing the compound obtained by the mixed extrusion in the step (I) into a special dipping die cavity, wherein the processing temperature of the dipping die cavity is 270-285 ℃. Then adopting a pultrusion process to uniformly infiltrate and wrap polypropylene resin on the surfaces of long glass fibers and flat long glass fibers which pass through a die cavity, finally cooling the infiltrated continuous glass fibers through a water tank, drawing, and then granulating by a granulator to obtain two types of long glass fiber particles with different lengths;
step three: and (3) uniformly mixing the two types of particles obtained in the step two according to a certain proportion to obtain the finished long glass fiber reinforced polypropylene composite material.
10. The method for preparing the multi-scale, low-warpage, high weld mark strength long glass fiber reinforced recycled polypropylene composite material according to claim 9, which is characterized in that: the processing temperature of the extruder in the first step is 235 ℃, and the rotating speed of a host machine is 270rpm; setting the temperature of the dipping tank at 280 ℃; the linear density of the long glass fiber reinforced recycled polypropylene is 2400Tex, and the grain cutting length is 4-6mm,6-8mm and 10-12mm.
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