CN115260655B - Polypropylene composite material and preparation method and application thereof - Google Patents

Polypropylene composite material and preparation method and application thereof Download PDF

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Publication number
CN115260655B
CN115260655B CN202210991669.6A CN202210991669A CN115260655B CN 115260655 B CN115260655 B CN 115260655B CN 202210991669 A CN202210991669 A CN 202210991669A CN 115260655 B CN115260655 B CN 115260655B
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polypropylene
composite material
polypropylene composite
melt
melt strength
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CN115260655A (en
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郝建鑫
袁海兵
秦小磊
邓爵安
黄泽彬
粟新
张聂斌
刘樟生
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Wuhu Selon New Material Technology Co ltd
Guangzhou Super Dragon Engineering Plastics Co ltd
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Wuhu Selon New Material Technology Co ltd
Guangzhou Super Dragon Engineering Plastics Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a polypropylene composite material and a preparation method and application thereof. The polypropylene composite material provided by the invention comprises the following components: polypropylene, melt strength modifier, thermoplastic elastomer, flame retardant, weather resistance agent, and laser absorber; the polypropylene is high melt strength polypropylene, the mass flow rate of the melt under the test condition of 2.16kg at 230 ℃ is 0.1-5 g/10min, and the melt strength modifier comprises at least one of high-density polyethylene, linear low-density polyethylene and low-density polyethylene. The large-size plastic-sucking workpiece prepared by the invention has the characteristics of high toughness, flame retardance, high and low temperature resistance, weather resistance, insulation and the like, and the integrated molding process of melt blending modification, extrusion of plates and negative pressure plastic sucking is adopted, so that the production efficiency is higher compared with the traditional production process.

Description

Polypropylene composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polypropylene composite material and a preparation method and application thereof.
Background
The electric automobile has become one of the important development directions of automobile industry at present, and compared with the traditional fuel automobile, the endurance mileage of single charging of the electric automobile is one of the important factors limiting the development of the electric automobile, and the battery pack is taken as an important core component of the electric automobile, so that the safety, the light weight and the low cost of the battery pack become important consideration factors. Currently, a bottom cover of a battery pack is generally formed by metal stamping, and for a material of an upper cover of the battery pack, there are mainly metal stamping, glass fiber reinforced thermosetting plastic (SMC, PCM, etc.) compression molding, injection molding of thermoplastic plastics, and other preparation methods. The metal material is gradually replaced by the polymer composite material due to its higher specific gravity and poor insulation and corrosion resistance; the glass fiber reinforced thermosetting plastic can not be recycled after being used, does not accord with the environmental protection low-carbon recycling economy development direction, and the defects of high material density, high processing cost and the like are gradually replaced by the thermoplastic plastic.
After the common polypropylene material is modified by strengthening, toughening, flame retarding and the like, the modified polypropylene material has the characteristics of balanced physical and mechanical properties, flame retarding, easiness in forming, low processing cost, simple process and the like, and can meet the severe requirements of the battery pack of the electric automobile. The glass fiber reinforced flame-retardant polyolefin composite material has the characteristics of high strength and excellent flame retardant property, but the material has lower processing fluidity, is not suitable for injection molding of large-sized battery pack upper covers with larger size, is only suitable for preparing large-sized battery pack upper covers in a compression molding mode with higher cost, and has appearance defects of easy appearance of floating fiber and the like on the surface. The prior art discloses a flame-retardant polypropylene material for a battery pack upper cover of a new energy vehicle and a preparation method thereof, wherein the material is produced by adopting a double-screw melt blending mode, and the glass fiber reinforced halogen-free flame-retardant polyolefin composite material is also low in processing fluidity, is unsuitable for forming a battery pack upper cover with a larger size, is low in temperature resistance of a halogen-free flame retardant, and is easy to cause appearance defects such as water lines, silver lines and the like for a dark battery pack upper cover. The prior art also discloses a battery pack upper cover of a new energy vehicle and a preparation method thereof, the patent mentions that thermoplastic (PP) is adopted for plastic suction molding, and mainly environmental-friendly flame retardant PP without halogen flame retardant is adopted for negative pressure plastic suction molding. Therefore, a material having excellent comprehensive properties and good workability and suitable for forming large-sized workpieces is desired.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the polypropylene composite material provided by the invention has the advantages of high toughness, flame retardance, high and low temperature resistance, weather resistance and good processability.
The invention also provides a preparation method and application of the polypropylene composite material.
In a first aspect of the present invention, a polypropylene composite is provided comprising the following components: polypropylene, melt strength modifier, thermoplastic elastomer, flame retardant, weather resistance agent, and laser absorber; the polypropylene is high melt strength polypropylene, the mass flow rate of the melt under the test condition of 2.16kg at 230 ℃ is 0.1-5 g/10min, and the melt strength modifier comprises at least one of high-density polyethylene, linear low-density polyethylene and low-density polyethylene.
According to the first aspect of the invention, at least the following beneficial effects are achieved:
the invention adopts high melt strength polypropylene as the basic component of the material, so that the material is endowed with good processing characteristics and balanced physical and mechanical properties; the melt strength modifier improves the melt strength of the composite material, effectively overcomes the defects of product breakage and serious wall thickness thinning during plastic suction molding, and simultaneously endows the material with good impact toughness; the thermoplastic elastomer improves the impact toughness of the material and improves the low temperature resistance of the material; the flame retardant mainly endows the material with good flame retardant property, so that the material can meet the safety requirement; the weather-proof agent can improve the outdoor service performance of the material, prevent the material from changing color and slow down the attenuation of the mechanical performance of the material; the laser absorber can endow the material with good laser energy absorption performance, realizes good marking definition, and the prepared polypropylene composite material has the performances of high toughness, flame retardance, high and low temperature resistance, weather resistance, insulation and the like, and has excellent processing performance.
Preferably, the polypropylene has a melt tension of 10 to 40cN, more preferably 14 to 30cN.
Preferably, the polypropylene comprises at least one of the grades HMSPP H001, HMSPP H-002.
Preferably, the melt strength modifier comprises high density polyethylene.
Preferably, the melt strength modifier has a melt mass flow rate of 0.1 to 10g/10min, more preferably 0.1 to 5g/10min, at 190℃under 2.16kg test conditions.
Preferably, the melt strength modifier comprises at least one of HDPE HHM5502, HDPE a5006FN 1280.
Preferably, the polypropylene composite material further comprises at least one of a filler, an antioxidant, a lubricant and a masterbatch. The filler can increase the strength and rigidity of the material, improve the dimensional stability of the product, and reduce the cost of the material; the antioxidant can prevent the high-temperature oxidative degradation of the material during processing, and simultaneously improve the oxidative degradation resistance of the material during use; the lubricant endows the material with good lubricating property, improves the dispersion property of the flame retardant and the filler of the material, reduces the friction between the material and the equipment cylinder, and improves the demoulding property and the appearance glossiness of the material.
Preferably, the polypropylene composite material comprises the following components in percentage by mass:
30-50% of polypropylene;
10-30% of melt strength modifier;
1-10% of thermoplastic elastomer;
20-40% of flame retardant;
0.1 to 1 percent of weather resistant agent;
0.1 to 2 percent of laser absorbent;
0-20% of filler;
0-1% of antioxidant;
0-1% of lubricant;
0-1% of color master batch.
Preferably, the polypropylene composite material comprises the following components in percentage by mass:
30-40% of polypropylene;
15-30% of melt strength modifier;
1 to 5 percent of thermoplastic elastomer;
20-30% of flame retardant;
0.1 to 0.5 percent of weather-proof agent;
0.3 to 1 percent of laser absorbent;
10-20% of filler;
0.1 to 1 percent of antioxidant;
0.1 to 0.5 percent of lubricant;
0-1% of color master batch.
Preferably, the polypropylene composite material comprises the following components in percentage by mass:
32-38% of polypropylene;
15-26% of melt strength modifier;
3-4% of thermoplastic elastomer;
27-30% of flame retardant;
0.1 to 0.2 percent of weather-proof agent;
0.3 to 0.5 percent of laser absorbent;
10-13% of filler;
0.1 to 0.2 percent of antioxidant;
0.2 to 0.3 percent of lubricant;
0-1% of color master batch.
Preferably, the thermoplastic elastomer comprises at least one of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), ethylene propylene diene rubber, methyl methacrylate-butadiene-styrene copolymer, ethylene-octene copolymer (POE), ethylene-acrylate copolymer, more preferably ethylene-octene copolymer (POE).
Preferably, the thermoplastic elastomer comprises a product under the trade designation POE LC 565.
Preferably, the flame retardant comprises a brominated flame retardant, and more preferably the flame retardant comprises at least one of decabromodiphenylethane and antimony trioxide.
Preferably, the flame retardant comprises decabromodiphenyl ethane and antimony trioxide, wherein the mass ratio of the decabromodiphenyl ethane to the antimony trioxide is 2.5-3.5: 1, more preferably 2.8 to 3.3:1.
Preferably, the flame retardant comprises decabromodiphenylethane, trade name RDT-3.
Preferably, the laser absorber is a metal compound that can efficiently absorb laser energy, preferably under the trademark LS-402.
Preferably, the filler comprises at least one of barium sulfate and talc, more preferably the filler comprises at least one of precipitated barium sulfate and talc MR-400A.
Preferably, the weather-resistant agent, the antioxidant, the lubricant and the color master batch are conventional commercial products in the industry.
The second aspect of the invention provides a preparation method of the polypropylene composite material, which comprises the following steps: and (3) carrying out melt blending on the components to obtain the polypropylene composite material.
The third aspect of the invention provides an application of the polypropylene composite material in preparing a plastic sucking workpiece, in particular to an application in preparing a large-size plastic sucking workpiece, comprising at least one of a battery pack upper cover, a roof trunk and a turnover tray.
The existing polypropylene composite material has the problems of low melt strength, difficult plastic suction forming and the like, is not suitable for workpieces with complex structures and large plastic suction depth, and has the defects that the surface of the workpiece obtained by plastic suction forming is easy to have surface silver marks, plastic suction holes and the like. The invention adopts high melt strength polypropylene as a main matrix and polyethylene as a melt strength modifier, so that the reduction rate of the wall thickness of the product can be effectively reduced, the defect of plastic sucking cracking is improved, and the large-size plastic sucking workpiece has better comprehensive performance.
Preferably, the surface area of the plastic uptake workpiece is equal to or greater than 1.4m 2, more preferably equal to or greater than 2.0m 2, and even more preferably equal to or greater than 2.5m 2.
Preferably, the surface area of the plastic uptake workpiece is 1 to 3m 2, more preferably 1.4 to 3m 2, still more preferably 1.5 to 2.6m 2.
Preferably, the depth of the plastic sucking workpiece is more than or equal to 15mm, more preferably more than or equal to 18mm, and further preferably more than or equal to 20mm.
Preferably, the depth of the blister workpiece is from 15 to 25mm, more preferably from 18 to 20mm.
The fourth aspect of the invention provides a method for preparing a plastic-sucking workpiece, comprising the following steps:
s1, melting, mixing and extruding all components of the polypropylene composite material to obtain a plate;
s2, carrying out negative pressure plastic suction molding on the plate to obtain a plastic suction workpiece.
Preferably, the area of the plate is equal to or more than 1.4m 2, more preferably the area of the plate is equal to or more than 2m 2, and even more preferably the area of the plate is equal to or more than 2.5m 2.
Preferably, the area of the sheet is 1.0 to 3.0m 2, more preferably 1.4 to 2.4m 2.
Preferably, the thickness of the plate is not less than 2.5mm, more preferably not less than 3.0mm, and still more preferably not less than 3.5mm.
Preferably, the thickness of the sheet is from 2 to 5mm, more preferably from 2 to 3.5mm.
Preferably, the sheet comprises a rectangular sheet having a length of 1.2 to 2m, more preferably 1.4 to 2m; the width is 1 to 1.5m, more preferably 1 to 1.2m.
Preferably, the melt mixing extrusion in the step S1 is implemented by a parallel twin screw extruder, and the length-diameter ratio of the screw is 40-50: 1, more preferably 48:1.
Preferably, the step S1 specifically comprises blending, melting and extruding the components of the polypropylene composite material, and obtaining the plate through a T-shaped die head, cooling and shaping, traction and cutting.
Preferably, the temperatures of each section of the extruder from the hopper to the die head are respectively 150～170℃、160～180℃、160～180℃、170～190℃、180～200℃、170～190℃、170～190℃、180～200℃、180～200℃、170～190℃、180～200℃、190～210℃.
Preferably, the temperatures of the sections of the extruder from the hopper to the die are 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃, 190 ℃ and 200 ℃, respectively.
Preferably, the screw speed of the extruder is 500-700 r/min. More preferably 600 to 700r/min.
Preferably, the frequency of the main port feed screw is 20 to 30Hz, more preferably 23 to 27Hz.
Preferably, the main body cylinder of the extruder is provided with two vacuum ports, and the vacuum degree is 500-600 mmHg, more preferably 550mmHg.
Preferably, the speed of the traction in step S1 is 1 to 2m/min, more preferably 1.2 to 1.8m/min.
Preferably, the step S2 is specifically to transfer the plate into a negative pressure plastic suction forming machine, bake, negative pressure plastic suction, cool and shape to obtain the plastic suction workpiece.
Preferably, the baking temperature is 180 to 220 ℃, more preferably 190 to 210 ℃. The baking time is 70 to 90 seconds, more preferably 80 to 90 seconds.
Preferably, the vacuum degree of the negative pressure suction molding is-0.01 to-0.1 MPa, more preferably-0.02 to-0.08 MPa.
Preferably, the cooling and shaping process further comprises punching and trimming after the plastic-sucking workpiece is obtained.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The invention adopts high melt strength polypropylene as a main matrix, has good melt strength, higher strength and excellent extrusion processing and forming performance compared with the conventional polypropylene material, can greatly improve and promote the defect that the conventional polypropylene material is difficult to be subjected to plastic suction forming, and particularly can effectively reduce the thinning rate of the wall thickness of a product for high-depth plastic suction products.
(2) The invention adopts polyethylene as a melt strength modifier, fully utilizes the characteristic that polyethylene has a lower melting point and a wider melting range than polypropylene, and can effectively improve the phenomenon of plastic sucking rupture caused by lower melt strength of polypropylene during plastic sucking forming processing.
(3) The invention adopts an integrated molding process of 'melt blending modification-extrusion plate-negative pressure plastic suction', compared with the traditional production process: firstly, preparing flame-retardant thermoplastic plastics, then transporting the flame-retardant thermoplastic plastics to a plate extrusion workshop for plate production, and then transporting the plate to a plastic-sucking molding factory for plastic-sucking molding of products; the integrated forming process has advancement, novelty and innovation, can adjust the material performance on line, and can control the quality of large-size workpieces (such as battery pack covers) on line in an integrated manner.
(4) Compared with the prior battery pack upper cover which adopts glass fiber reinforced thermosetting plastic, the large-size workpiece (such as the battery pack upper cover of the electric automobile) prepared by the invention has the characteristics of high toughness, flame retardance, high and low temperature resistance, weather resistance, insulation and the like, and the product has the characteristics of easy molding, low equipment investment cost, high processing efficiency, low processing cost, recycling and the like; compared with the injection molding battery pack upper cover, the product has the characteristics of convenience in molding, low processing cost and applicability to large-size battery pack upper covers.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment adopts polypropylene composite material to prepare an upper cover product of the battery pack of the electric automobile, and the specific process is as follows:
The following components are accurately weighed according to a certain proportion: high melt strength polypropylene 37% (brand: HMSPP H-001, china petrochemical Co., ltd.), melt strength modifier 15% (brand: HDPE HHM5502, china petrochemical Co., ltd.), thermoplastic elastomer 3.9% (brand: POE LC565, korean LG chemical Co., ltd.), flame retardant 30% (decabromodiphenyl ethane, 23%, brand: RDT-3, shore Wei Dong chemical Co., ltd.; antimony trioxide, 7%, chang Dechen state antimony Co., ltd.), filler 13% (precipitated barium sulfate, mars (New Shang) fine chemical Co., ltd.), weathering agent 0.1% (commercially available), laser absorber 0.5% (brand: LS-402, aika effect pigment (bead sea Co., ltd.), antioxidant 0.2% (commercially available), lubricant 0.3% (commercially available).
After the materials are weighed, the materials are added into a high-speed stirrer to be stirred uniformly, then the materials are added into a main feeding hopper of a parallel double-screw extruder with the length-diameter ratio of 48:1, and the temperatures of all sections of the extruder from the hopper to a die head are set to be respectively (12 areas in total): 160 ℃,170 ℃,170 ℃,180 ℃,190 ℃,180 ℃,180 ℃,190 ℃,190 ℃,200 ℃ and the screw speed of a main machine are 650r/min, the frequency of a feeding screw of a main hopper is 23Hz, two vacuum ports are formed in a main machine cylinder, the vacuum degree is 550mmHg, materials are mixed, melted and extruded, a T-shaped die head, a cooling roller is used for shaping, cooling and traction, the traction speed is set to be 1.5m/min, a flame-retardant polyolefin plate with the thickness of 3.5mm is prepared, the continuously extruded plate is cut into a rectangular plate with the length of 2.0m and the width of 1.2m on line, then the plate is transferred into a negative pressure plastic sucking forming machine, the baking temperature is set to 210 ℃, the baking time is 85s, the vacuum degree is-0.08 MPa, negative pressure plastic sucking is carried out, cooling and shaping is carried out, so that a battery pack upper cover blank is obtained, and then punching and trimming are carried out through a numerical control machine (CNC) to obtain an electric automobile battery pack upper cover product (length of 2.0m, width of 1.2m and depth of 18 mm).
Example 2
The embodiment adopts polypropylene composite material to prepare an upper cover product of the battery pack of the electric automobile, and the specific process is as follows:
the following components are accurately weighed according to a certain proportion: high melt strength polypropylene 38% (brand: HMSPP H-002, china petrochemical Co., ltd.) melt strength modifier 17% (brand: HDPE HHM5502, china petrochemical Co., ltd.), thermoplastic elastomer 3.9% (brand: POE LC565, korean LG chemical Co., ltd.), flame retardant 30% (decabromodiphenyl ethane 23%, brand: RDT-3, shouguang Wei Dong chemical Co., ltd.; antimony trioxide, 7%, chang Dechen state antimony Co., ltd.), filler 10% (talc MR-400A, liaoning North sea Co., ltd.), weathering agent 0.1% (commercially available), laser absorber 0.5% (brand: LS-402, aika effect pigment (pearl sea Co., ltd.), antioxidant 0.2% (commercially available), lubricant 0.3% (commercially available).
After the materials are weighed, the materials are added into a high-speed stirrer to be stirred uniformly, then the materials are added into a main feeding hopper of a parallel double-screw extruder with the length-diameter ratio of 48:1, and the temperatures of all sections of the extruder from the hopper to a die head are set to be respectively (12 areas in total): 160 ℃,170 ℃,170 ℃,180 ℃,190 ℃,180 ℃,180 ℃,190 ℃,190 ℃,200 ℃ and 600r/min of screw speed of a main machine hopper, 27Hz of frequency of a feeding screw of a main machine hopper, two vacuum ports on a main machine barrel, 550mmHg of vacuum degree, blending, melting and extruding materials, shaping, cooling and pulling through a T-shaped die head and a cooling roller, setting the pulling speed to be 1.2m/min, preparing a flame-retardant polyolefin plate with the thickness of 3.0mm, cutting the continuously extruded plate into a rectangular plate with the length of 1.8m and the width of 1.1m on line, transferring the plate into a negative pressure plastic sucking forming machine, setting the baking temperature to 190 ℃, baking time to be 88s, carrying out negative pressure plastic sucking at the vacuum degree of-0.05 MPa, cooling and shaping to obtain a battery pack upper cover blank, and then punching and trimming through a numerical control machine (CNC) to obtain an electric automobile battery pack upper cover product (length of 1.8m, width of 1.1m and depth of 18 mm).
Example 3
The embodiment adopts polypropylene composite material to prepare an upper cover product of the battery pack of the electric automobile, and the specific process is as follows:
The following components are accurately weighed according to a certain proportion: high melt strength polypropylene 32% (brand: HMSPP H-002, beijing Yanshan petrochemical Co., ltd.) of the petrochemical group of China, melt strength modifier 26% (brand: HDPE A5006FN1280, mitsu petrochemical Co., ltd.), thermoplastic elastomer 3.9% (brand: POE LC565, korean LG chemical Co., ltd.), flame retardant 27% (decabromodiphenyl ethane, 20%, brand: RDT-3, shore Wei Dong chemical Co., ltd.; antimony trioxide, 7%, chang Dechen state antimony Co., ltd.), filler 10% (talc MR-400A, liaoning North sea Co., ltd.), weathering agent 0.2% (commercially available), laser absorber 0.5% (brand: LS-402, aika effect pigment (pearl sea Co., ltd.), antioxidant 0.2% (commercially available), lubricant 0.2% (commercially available).
After the materials are weighed, the materials are added into a high-speed stirrer to be stirred uniformly, then the materials are added into a main feeding hopper of a parallel double-screw extruder with the length-diameter ratio of 48:1, and the temperatures of all sections of the extruder from the hopper to a die head are set to be respectively (12 areas in total): 160 ℃,170 ℃,170 ℃,180 ℃,190 ℃,180 ℃,180 ℃,190 ℃,190 ℃,200 ℃ and 600r/min of screw speed of a main machine hopper, 27Hz of frequency of a feeding screw of a main machine hopper, two vacuum ports on a main machine barrel, 550mmHg of vacuum degree, blending, melting and extruding materials, shaping, cooling and pulling through a T-shaped die head and a cooling roller, setting the pulling speed to be 1.8m/min, preparing a flame-retardant polyolefin plate with the thickness of 2.5mm, cutting the continuously extruded plate into a rectangular plate with the length of 1.4m and the width of 1.0m on line, transferring the plate into a negative pressure plastic sucking forming machine, setting the baking temperature to 220 ℃, baking time to be 81s, carrying out negative pressure plastic sucking with the vacuum degree of-0.02 MPa, cooling and shaping to obtain a battery pack upper cover blank, and then punching and trimming through a numerical control machine (CNC) to obtain an electric automobile battery pack upper cover product (with the length of 1.4m, the width of 1.0m and the depth of 20 mm).
Table 1A list of the amounts (mass%) of the components in examples 1 to 3
Example 1 Example 2 Example 3
Polypropylene 37 38 32
Melt strength modifier 15 17 26
Thermoplastic elastomer 3.9 3.9 3.9
Flame retardant 30 30 27
Packing material 13 10 10
Weather-proof agent 0.1 0.1 0.2
Laser absorber 0.5 0.5 0.5
Antioxidant 0.2 0.2 0.2
Lubricant 0.3 0.3 0.2
Comparative example 1
The comparative example was a battery top cover product for an electric vehicle, which was prepared using a polypropylene composite material, and was different from example 1 in that the high melt strength polypropylene of example 1 was replaced with conventional polypropylene (trade name: Z30S, china petrochemical Co., ltd.) and the specific procedure was similar to that of example 1.
Comparative example 2
The comparative example used polypropylene composite material to prepare an upper cover product for an electric vehicle battery, which is different from example 2 in that the melt strength modifier was omitted, namely, equal amount of high melt strength polypropylene (brand: HMSPP H-002, beijing Yanshan petrochemical Co., ltd.) was used instead of the melt strength modifier, and the specific procedure was similar to example 2.
Comparative example 3
The comparative example adopts polypropylene composite material to prepare an upper cover product of the electric automobile battery, and the difference from the example 3 is that the integrated molding process of melt blending modification, extrusion of plate material and negative pressure plastic suction is not adopted, but polyolefin composite material granules are prepared firstly, then the plate material is prepared by using the granules, and then the upper cover product of the electric automobile battery is obtained by negative pressure plastic suction. The types and amounts of the components were similar to those of example 3, and the preparation process was as follows:
after accurately weighing the materials, adding the materials into a high-speed stirrer for stirring uniformly, then adding the materials into a main feeding hopper of a parallel double-screw extruder with the length-diameter ratio of 48:1, and setting the temperatures of each section of the extruder from the hopper to a die head to be respectively (12 sections in total): 160 ℃,170 ℃,170 ℃,180 ℃,190 ℃,180 ℃,180 ℃,180 ℃,190 ℃,190 ℃,200 ℃ and the screw speed of a main machine are 600r/min, the frequency of a feeding screw of a main hopper is 27Hz, two vacuum ports are arranged on a main machine cylinder body, the vacuum degree is 550mmHg, the materials are mixed and melted and extruded, the grain strips obtained through the port die are cooled by a water tank and blown dry by a fan, and then enter a grain cutter for grain cutting, so that the flame-retardant polyolefin composite material for the battery pack upper cover of the electric automobile with the length of 3-5 mm can be obtained.
The flame-retardant polyolefin composite material is dried for 2 hours at 110 ℃, then is added into a single screw hopper, the temperature of each section of an extruder is set to be 180-220 ℃, a melt is extruded through a T-shaped die, a cooling roller is used for shaping, cooling and traction, the traction speed is set to be 1.8m/min, a flame-retardant polyolefin plate with the thickness of 2.5mm is prepared, and the plate is cut into a rectangular plate with the length of 1.4m and the width of 1.0m on line.
Placing the plate into a negative pressure plastic suction forming machine, setting a baking temperature of 220 ℃, a baking time of 81s and a vacuum degree of-0.02 MPa for negative pressure plastic suction, cooling and shaping to obtain a blank of the battery pack upper cover, and then punching and trimming by a numerical control machine (CNC) to obtain an electric automobile battery pack upper cover product (length 1.4m, width 1.0m and depth 20 mm).
Comparative example 4
The comparative example used polypropylene composite material to prepare a battery pack upper cover product for an electric vehicle, which is different from example 1 in that filler (precipitated barium sulfate, red star (new shake) fine chemistry liability company) was replaced with an equal amount of short glass fiber (trade mark: ECS305-4.5-K, chongqing International composite material Co., ltd.) as follows:
High melt strength polypropylene 37% (brand: HMSPP H-001, china petrochemical Co., ltd.), melt strength modifier 15% (brand: HDPE HHM5502, china petrochemical Co., ltd.), thermoplastic elastomer 3.9% (brand: POE LC565, korean LG chemical Co., ltd.), flame retardant 30% (decabromodiphenyl ethane 23%, brand: RDT-3, shouguang Wei Dong chemical Co., ltd.; antimony trioxide 7%, chang Dechen state antimony Co., ltd.), short glass fiber 13% (brand: ECS305-4.5-K, chongqing International composite Co., ltd.), weathering agent 0.1% (commercially available), laser absorber 0.5% (brand: LS-402, aika special effect pigment (pearl sea Co., ltd.), 0.2% (commercially available) and lubricant 0.3% (commercially available).
After the materials are weighed (except for short glass fibers), the materials are added into a high-speed stirrer for uniform stirring, then the materials are added into a main feeding hopper of a parallel double-screw extruder with the length-diameter ratio of 48:1, the short glass fibers are added from a side feeding hopper of the parallel double-screw extruder, and the temperatures of all sections from the hopper to a die head of the extruder are respectively set to be (12 areas in total): 160 ℃,170 ℃,170 ℃,180 ℃,190 ℃,180 ℃,180 ℃,190 ℃,190 ℃,190 ℃ 200 ℃ and 650r/min of screw speed of a main machine, 23Hz of frequency of a main hopper feeding screw, 5Hz of frequency of a side feeding hopper feeding screw, two vacuum ports on a main machine cylinder, 550mmHg of vacuum degree, blending materials, melting and extruding, shaping by a T-shaped die head, a cooling roller, cooling, traction, setting the traction speed to be 1.5m/min, preparing a flame-retardant polyolefin plate with the thickness of 3.5mm, cutting the continuously extruded plate into a rectangular plate with the length of 2.0m and the width of 1.2m on line, transferring the plate into a negative pressure plastic sucking forming machine, setting the baking temperature to be 220 ℃ for 92s, carrying out negative pressure plastic sucking on the plate with the vacuum degree of-0.08 MPa, cooling and shaping to obtain a blank of a battery pack upper cover, and then punching and trimming by a CNC machine tool (CNC) to obtain a battery pack upper cover product of an electric automobile.
Test examples
The performance of the upper cover of the battery pack of the electric automobile prepared by the embodiment and the comparative example is tested by the test example, wherein the calculation formula of the corner thickness reduction rate is as follows: corner thickness reduction rate= (planar thickness-corner thickness) ×100%/planar thickness.
Table 2 performance of battery top covers for electric vehicles prepared in examples and comparative examples
As shown in Table 2, the large-size upper cover of the electric automobile battery prepared by the invention has better comprehensive mechanical property, the tensile strength is more than or equal to 15.9MPa, the notch impact strength of the cantilever beam is more than or equal to 23.4MPa, the bending strength is more than or equal to 18.2MPa, the bending modulus is more than or equal to 834MPa, and the flame retardant grade can reach V0 level, and the integrated molding process of melt blending modification-extrusion plate-negative pressure plastic suction is adopted, so that the processing efficiency can be effectively improved, the production cost is reduced, and the large-scale production is suitable. In contrast, in comparative example 1, the tensile strength of the upper cover product of the electric automobile prepared from the common polypropylene is obviously reduced, the notch impact strength of the cantilever beam is obviously reduced, the processability is poor, and the processing efficiency is reduced. Comparative example 2 omits the melt strength modifier and the molding processability becomes poor. In the comparative example 3, polyolefin composite material granules are prepared firstly, then the granules are used for preparing plates, and then negative pressure plastic suction is performed to obtain the upper cover product of the electric automobile battery, so that the production efficiency is drastically reduced, and the requirement of mass production cannot be met. In comparative example 4, short glass fibers were used instead of fillers, but the tensile strength, bending strength and bending modulus were increased, but the notched impact strength of the cantilever was poor, the toughness was insufficient, the comprehensive mechanical properties were poor, and the molding processability was remarkably deteriorated due to the addition of the short glass fibers, and the production efficiency was lowered.

Claims (5)

1. The polypropylene composite material is characterized by being prepared from the following components in percentage by mass:
32% of polypropylene;
26% of a melt strength modifier;
3.9% of a thermoplastic elastomer;
27% of flame retardant;
0.2% of weather-proof agent;
0.5% of a laser absorber;
10% of filler;
0.2% of antioxidant;
0.2% of a lubricant;
the polypropylene is high melt strength polypropylene, and the mass flow rate of the melt under the test condition of 2.16kg at 230 ℃ is 0.1-5 g/10min;
The melt tension of the polypropylene is 10-40 cN;
The melt strength modifier comprises at least one of high-density polyethylene, linear low-density polyethylene and low-density polyethylene, and the mass flow rate of the melt under the test condition of 2.16kg at 190 ℃ is 0.1-10 g/10min;
The filler comprises at least one of barium sulfate and talcum powder;
the polypropylene composite material is prepared by a preparation method comprising the following steps: and (3) carrying out melt blending on the components to obtain the polypropylene composite material.
2. Use of the polypropylene composite according to claim 1 for the preparation of a blister workpiece.
3. The use according to claim 2, wherein the surface area of the plastic-absorbing workpiece is not less than 1.4m 2; the depth is more than or equal to 15mm.
4. The preparation method of the plastic-sucking workpiece is characterized by comprising the following steps of:
s1, melting, mixing and extruding all components of the polypropylene composite material to obtain a plate;
S2, carrying out negative pressure plastic suction molding on the plate to obtain a plastic suction workpiece;
The polypropylene composite is the polypropylene composite of claim 1.
5. The method according to claim 4, wherein the area of the plate is 1.4m 2 or more; the thickness is more than or equal to 2.5mm.
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CN115160688A (en) * 2022-06-29 2022-10-11 广州市聚赛龙工程塑料股份有限公司 Flame-retardant polypropylene composite material for new energy automobile battery pack upper cover and preparation method thereof

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CN105670113A (en) * 2016-02-23 2016-06-15 佛山市美聚克化工科技有限公司 Low-temperature-resisting and fireproof polypropylene sheet material capable of easily sucking plastic
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