CN110643117A - Low-processing-viscosity matte TPO skin material, and preparation method and application thereof - Google Patents
Low-processing-viscosity matte TPO skin material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a low processing viscosity matte TPO (thermoplastic polyolefin) skin material, a preparation method and application thereof, wherein the TPO skin material is obtained by filling thermoplastic polyolefin TPO and nano particles in a mass ratio of 90-99.5: 0.5-10; the nano particles comprise one or more of multi-layer graphene, carbon nano tubes, monodisperse polystyrene microspheres, manganese oxide nano wires, ferroferric oxide nano particles, gas-phase silicon dioxide and nano carbon black particles. The filling of the nano particles increases the free volume of the polymer, reduces the density of entanglement points, simultaneously generates interfacial slippage between the nano particles and macromolecules, and is equivalent to the action of a lubricant to reduce the viscosity of a system, thereby reducing the process temperature of operations such as mixing, calendering, extruding and the like in the material processing process. The nano particles have an extinction effect; the addition of the nano particles has little influence on the mechanical properties of the material, improves the wear-resistant coefficient and provides guidance for industrial production.
Description
Technical Field
The invention belongs to the technical field of automobile materials, and particularly relates to a low-processing-viscosity matte TPO skin material, and a preparation method and application thereof.
Background
Automobile instrument panels are important components of automobile interior trim. The instrument panel is a very unique part integrating safety, functionality, comfort and decoration. The instrument panel can be divided into a hard plastic instrument panel and a soft instrument panel. In middle and high-grade automobiles, polyvinyl chloride (PVC), Thermoplastic Polyurethane (TPU), Thermoplastic Polyolefin (TPO), and the like are generally used as polymer materials for the skin of an automobile soft instrument panel. The PVC skin is low in price, but the problems of excessive VOC and the like exist. TPU has very good overall properties, but is relatively expensive and is usually used in high-grade automobiles. The TPO skin has the characteristics of low VOC and lower price than TPU, so that the TPO automobile instrument panel skin is greatly developed under the condition that the VOC content of the current automobile interior has clear regulatory requirements, and has a good market prospect.
Currently, in order to improve the recycling and comfort of automotive interior materials and meet low VOC emission standards, conventional PVC skin materials are gradually replaced with polyolefin thermoplastic elastomers TPO, which are easily recycled, have advantages of low cost, low density, good chemical resistance, and the like, and have been widely used as instrument panel skins, automobile bumpers, rain shields, and other automotive parts.
In the prior art, industrial production of TPO skins still has many technical difficulties. Chinese patent CN 107351495A proposes a multicolor TPO automotive interior material and a preparation method thereof. Firstly, preparing a single-color TPO skin, splicing and compounding the single-color TPO skin by a compound machine to obtain a multi-color TPO skin layer, then carrying out corona treatment, coating a layer of water-based polyurethane coating, and compounding the water-based polyurethane coating and polyolefin sponge into an automotive interior material. Wherein, the polyurethane coating is coated after corona treatment to improve the matte performance and the wear resistance of the TPO skin. Because, corona treatment in the production process can release ozone to cause harm to workers, leading to environmental problems. Meanwhile, the poor corona effect can be caused by the reasons of electric leakage and the like in the corona process, the qualification rate of TPO materials is reduced, and the production cost is increased. Chinese patent CN 107323046 a adopts adhesive to replace corona treatment, firstly synthesizes TPO cast film by extruder, then compounds with polypropylene foam under pressure, then coats adhesive, surface treatment agent, etc., although corona process is avoided in the operation process, multi-layer material compounding, process operation is complex, simultaneously, cast film temperature is up to 220 ℃, pressure is up to 6Mpa, affects the definition of skin pattern. Chinese patent CN 106827751A proposes an environment-friendly automotive interior composite material and a preparation method thereof, wherein the temperature in the preparation process is up to 250 ℃, and the head temperature is up to 270 ℃. The patterns of the surface skin can be greatly influenced under the high-temperature condition. Chinese patent CN 102514337 discloses an interior material for automobile and a manufacturing method thereof, wherein TPO is subjected to two calendering and banburying processes, and the material is very difficult to peel off from a roll due to the excessive temperature, which causes the problems of uneven thickness and uneven surface, and thus the use requirement cannot be met.
TPO is an important thermoplastic elastomer, and has elasticity and thermoplasticity, and can be softened and melted after being heated, and then can be subjected to injection molding, extrusion and blow molding. But the production process needs higher extrusion temperature, higher calendering temperature and higher plastic uptake temperature to process, thus increasing energy consumption. At present, how to reduce the processing viscosity and control the processing temperature becomes an important problem of the process production. Good processability tends to result in a reduction in mechanical properties. As an automobile interior material, in order to avoid the problem of traffic safety caused by glass reflection, a matte design is adopted in principle, and the problems of high surface glossiness, poor wear resistance, no matte and the like of a TPO material are solved, so that the TPO material needs to be subjected to corona treatment or operations of coating an adhesive, a surface treating agent and the like, and the performance causes limitation in the actual production and application processes. The problem of how to reduce the processing viscosity without influencing the mechanical property of the material and simultaneously reduce the glossiness of the material per se can bring important significance to industrial production.
Disclosure of Invention
In view of the above, the present invention aims to provide a low processing viscosity matte TPO skin material, a preparation method and an application thereof, wherein the processing temperature of the TPO skin material is low.
The invention provides a low-processing viscosity matte TPO (thermoplastic polyolefin) skin material, which comprises the following components in percentage by mass of 90-99.5: 0.5-10 parts of thermoplastic polyolefin TPO and nano particles;
the nano particles are selected from one or more of multi-layer graphene, carbon nano tubes, monodisperse polystyrene microspheres, manganese oxide nano wires, ferroferric oxide nano particles, gas-phase silica and nano carbon black particles.
Preferably, the multilayer graphene has the thickness of 1-3 nm, the diameter of 3-5 microns, the number of layers of 2-5 layers and the specific surface area of 480-520 m2/g；
The diameter of the carbon nano tube is 6-8 nm, and the length of the carbon nano tube is 48-52 mu m;
the diameter of the monodisperse polystyrene microsphere is 5-10 nm;
the diameter of the manganese oxide nanowire is 9-11 nm;
the particle size of the ferroferric oxide nano particles is 9-11 nm;
the particle size of the fumed silica is 5-10 nm;
the particle size of the nano carbon black particles is 5-10 nm.
Preferably, the thermoplastic polyolefin TPO comprises the following components in a mass ratio of 30-60: 1-40: 1-30: 0.1-1: 0.05-5: 0.1-3 of rubber, polyolefin resin, elastomer, ultraviolet absorber, antioxidant, carbon black and flame retardant.
Preferably, the rubber is selected from one or more of ethylene propylene rubber, ethylene propylene diene monomer rubber, styrene butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, thermoplastic dynamic fully vulcanized rubber, polyurethane elastomer and fluororubber;
the polyolefin resin is selected from one or more of polyethylene, polypropylene, polyisobutylene, poly 4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer;
the elastomer is selected from ethylene elastomers and/or styrene elastomers.
Preferably, the polypropylene has a melt index of 20g/10 min; the polyethylene is selected from low density polyethylene with a melt index of 10g/10 min.
Preferably, the ethylene-based elastomer is selected from one or more of ethylene/octene copolymers, olefin block copolymers, ethylene/propylene copolymers and ethylene/propylene/butadiene copolymers;
the styrene elastomer is selected from one or more of styrene/butadiene/styrene block copolymer, hydrogenated styrene/butadiene/styrene block copolymer, styrene/isoprene/styrene block copolymer, styrene/hexene-butene/styrene block copolymer and styrene/ethylene-propylene/styrene block copolymer.
Preferably, the rubber is selected from one or more of ethylene propylene diene monomer rubber with the model number FG1901, thermoplastic dynamic fully vulcanized rubber with the model number 251-70W232 and polyurethane elastomer with the model number 385E;
the polyolefin resin is selected from one or more of polyolefin resin type 101-73, polypropylene type 1120, and low density polyethylene type 5021 DX;
the elastomer is selected from styrene/hexene-butene/styrene block copolymers of type G1650M and/or ethylene/octene copolymers of type LG LC 175.
Preferably, the ultraviolet light absorbers comprise bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate and/or poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate;
the antioxidant comprises tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid ] pentaerythritol ester antioxidant and/or octadecyl 3, 5-di-tert-butyl-4-hydroxyphenyl propionate antioxidant;
the model of the carbon black is MCF-88;
the flame retardant is selected from triphenyl phosphate.
The invention provides a preparation method of the TPO skin material in the technical scheme, which comprises the following steps:
and (2) mixing the components in a mass ratio of 90-99.5: and (3) mixing 0.5-10 of thermoplastic polyolefin TPO and the nano particles at 180-230 ℃ for 7-9 min to obtain the low-processing-viscosity matte TPO skin material.
The invention provides an application of the low processing viscosity matte TPO skin material in the technical scheme or the low processing viscosity matte TPO skin material prepared by the preparation method in the technical scheme in an automotive interior material.
The invention provides a low-processing viscosity matte TPO (thermoplastic polyolefin) skin material, which comprises the following components in percentage by mass of 90-99.5: 0.5-10 parts of thermoplastic polyolefin TPO and nano particles; the nano particles are selected from one or more of multi-layer graphene, carbon nano tubes, monodisperse polystyrene microspheres, manganese oxide nano wires, ferroferric oxide nano particles, gas-phase silica and nano carbon black particles. The invention adopts the nano particles to be filled in the thermoplastic polyolefin TPO, increases the free volume of the polymer, reduces the entanglement density, simultaneously generates interface slippage between the nano particles and macromolecules, and is equivalent to the action of a lubricant to reduce the viscosity of a system, thereby reducing the process temperature of operations such as mixing, calendering, extruding and the like in the material processing process and fundamentally solving a series of problems caused by overhigh material temperature in the industrial production process. The nano particles also have the extinction effect, reduce the glossiness of the material and make the surface of the material matte; the addition of the nano particles has little influence on the mechanical properties of the material, improves the wear resistance coefficient and provides a guiding significance for industrial production. The experimental results show that: the viscosity of the TPO skin material added with the nano particles is reduced by more than 25 percent compared with the TPO skin material without the nano particles, so that operations such as mixing, rolling, extruding and the like can be carried out at lower temperature, and simultaneously, the glossiness of the TPO skin material added with the nano particles meets the matte requirement of the automobile instrument panel skin: the glossiness is less than 3.5, 60 ℃ method, QC/29089-.
Drawings
FIG. 1 is a graph showing the change in viscosity at 160 ℃ of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1;
FIG. 2 is a matte test chart of TPO skin materials prepared in examples 1-3 of the present invention and comparative example 1.
Detailed Description
The invention provides a low-processing viscosity matte TPO (thermoplastic polyolefin) skin material, which comprises the following components in percentage by mass of 90-99.5: 0.5-10 parts of thermoplastic polyolefin TPO and nano particles;
the nano particles are selected from one or more of multi-layer graphene, carbon nano tubes, monodisperse polystyrene microspheres, manganese oxide nano wires, ferroferric oxide nano particles, gas-phase silica and nano carbon black particles.
The invention adopts the nano particles to be filled in the thermoplastic polyolefin TPO, increases the free volume of the polymer, reduces the entanglement density, simultaneously generates interface slippage between the nano particles and macromolecules, and is equivalent to the action of a lubricant to reduce the viscosity of a system, thereby reducing the process temperature of operations such as mixing, calendering, extruding and the like in the material processing process and fundamentally solving a series of problems caused by overhigh material temperature in the industrial production process. The nano particles also have the extinction effect, reduce the glossiness of the material and make the surface of the material matte; the addition of the nano particles has little influence on the mechanical properties of the material, improves the wear resistance coefficient and provides a guiding significance for industrial production.
The low processing viscosity matte TPO skin material provided by the invention comprises thermoplastic polyolefin TPO. In the invention, the thermoplastic polyolefin TPO is a dynamic partially vulcanized blending type, comprises rubber, polyolefin resin, elastomer and other auxiliary agents, and has an uneven two-phase structure; the physically crosslinked regions exhibit thermoplastic flow properties, which combine the dual properties of rubber and plastic.
In the invention, the thermoplastic polyolefin TPO comprises the following components in a mass ratio of 30-60: 1-40: 1-30: 0.1-1: 0.05-5: 0.1-3 of rubber, polyolefin resin, elastomer, ultraviolet absorber, antioxidant, carbon black and flame retardant, preferably 40-50: 15-35: 10-30: 0.1-0.5: 0.05-5: 0.1-2. In a specific embodiment, the thermoplastic polyolefin TPO includes a rubber, a polyolefin resin, an elastomer, an ultraviolet light absorber, an antioxidant, carbon black, and a flame retardant in a mass ratio of 40:30:20:0.25:0.25:3.5: 1.
In the present invention, the rubber is selected from one or more of Ethylene Propylene Rubber (EPR), ethylene propylene diene monomer rubber (EPDM), Styrene Butadiene Rubber (SBR), chloroprene rubber, Nitrile Butadiene Rubber (NBR), butyl rubber (IIR), thermoplastic dynamic fully vulcanized rubber (TPV), polyurethane elastomer (TPU), and fluororubber; the polyolefin resin is selected from one or more of Polyethylene (PE), polypropylene (PP), Polyisobutylene (PIB), poly (4-methyl-1-pentene) (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer; the elastomer is selected from ethylene elastomers and/or styrene elastomers.
The polyethylene comprises one or more of LDPE, MDPE, HDPE and LLDPE;
the polypropylene comprises one or more of atactic PP, isotactic PP and syndiotactic PP. The polypropylene has low volatility, high viscosity index, low pour point, high flash point and good high temperature oxidation performance.
In a specific embodiment of the invention, the polypropylene has a melt index of 20g/10 min; the polyethylene is selected from low density polyethylene with a melt index of 10g/10 min.
In the present invention, the ethylene-based elastomer is selected from one or more of ethylene/octene copolymers (POE), Olefin Block Copolymers (OBC), ethylene/propylene copolymers (EPM) and ethylene/propylene/butadiene copolymers (EPDM);
the styrene-based elastomer is preferably selected from one or more of styrene/butadiene/styrene block copolymer (SBS), hydrogenated styrene/butadiene/styrene block copolymer (SEBS), styrene/isoprene/styrene block copolymer (SIS), styrene/hexene-butene/styrene block copolymer and styrene/ethylene-propylene/styrene block copolymer, and more preferably from styrene/ethylene/butene block copolymer (SEBS) and/or ethylene/octene copolymer (POE).
In the invention, the POE is a thermoplastic elastomer which adopts metallocene catalyst and realizes in-situ polymerization of ethylene and octene, and has excellent toughness and good processability. The POE has no unsaturated double bond in the molecular structure, excellent ageing resistance, narrow molecular weight distribution, good flowability and good compatibility with polyolefin. The material has higher impact strength and elongation at break.
In a particular embodiment of the invention, the rubber is selected from one or more of ethylene propylene diene monomer rubber of type FG1901, thermoplastic dynamic fully vulcanized rubber of type 251-70W232 and polyurethane elastomer of type 385E; the polyolefin resin is selected from one or more of polyolefin resin type 101-73, polypropylene type 1120, and low density polyethylene type 5021 DX; the elastomer is selected from styrene/hexene-butene/styrene block copolymers of type G1650M and/or ethylene/octene copolymers of type LG LC 175. The ultraviolet light absorber comprises bis (1,2,2,6, 6-pentamethyl-4 piperidyl) sebacate) and/or poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate); in particular embodiments, the ultraviolet light absorber is selected from Tinuvin 292, BASF, germany, and/or Tinuvin622SF, BASF, germany. The antioxidant preferably comprises tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid ] pentaerythritol ester antioxidant) and/or octadecyl 3, 5-di-tert-butyl-4-hydroxyphenyl propionate antioxidant); in a specific embodiment, the antioxidant is selected from Irganox 1010 from BASF, germany and/or Irganox 1076 from BASF, germany. The model of the carbon black is MCF-88; the flame retardant is selected from triphenyl phosphate; in a specific embodiment, the flame retardant is selected from the group consisting of DisflamolTP from Langsheng, Germany.
The low processing viscosity matte TPO skin material provided by the invention comprises nanoparticles, wherein the nanoparticles are filled in the thermoplastic polyolefin TPO; the nano particles are selected from one or more of multi-layer graphene, carbon nano tubes, monodisperse polystyrene microspheres, manganese oxide nano wires, ferroferric oxide nano particles, gas-phase silica and nano carbon black particles. The particle size among the nano particles is smaller than the mean square radius of gyration of the polymer, and the nano particles are uniformly distributed in the system, so that the viscosity reduction behavior of a high molecular system occurs. In the invention, the refractive index of the fumed silica is 1.46, is close to that of the resin, can obviously reduce the surface gloss of the material, and is a good flatting agent.
In the invention, the multilayer graphene has the thickness of 1-3 nm, the diameter of 3-5 microns, the number of layers of 2-5 layers and the specific surface area of 480-520 m2/g；
The diameter of the carbon nano tube is 6-8 nm, and the length of the carbon nano tube is 48-52 mu m;
the diameter of the monodisperse polystyrene microsphere is 5-10 nm;
the diameter of the manganese oxide nanowire is 9-11 nm;
the particle size of the ferroferric oxide nano particles is 9-11 nm;
the particle size of the fumed silica is 5-10 nm;
the particle size of the nano carbon black particles is 5-10 nm.
In the present invention, the monodisperse polystyrene microsphere is preferably prepared according to the following method:
mixing water, hydrophobic monomer styrene, a dispersing agent and a pH regulator sodium bicarbonate, exhausting air, heating, adding an initiator potassium persulfate to react to obtain polystyrene emulsion, and drying to obtain the monodisperse polystyrene microsphere.
In the present invention, the dispersant is preferably selected from Luborun corporation
2700 dispersing agent.
In the invention, the mass ratio of the thermoplastic polyolefin TPO to the nanoparticles is 90-99.5: 0.5-10, preferably 92-98: 2-8, more preferably 94-97: 3-6; in a specific embodiment, the thermoplastic polyolefin TPO and nanoparticles are present in a mass ratio of 95: 5.
The invention provides a preparation method of the TPO skin material in the technical scheme, which comprises the following steps:
and (2) mixing the components in a mass ratio of 90-99.5: and (3) mixing 0.5-10 of thermoplastic polyolefin TPO and the nano particles at 180-230 ℃ for 7-9 min to obtain the low-processing-viscosity matte TPO skin material.
The invention preferably mixes under the condition of stirring, and the stirring speed is preferably 180-220 rpm, more preferably 190-210 rpm; in a specific embodiment, the stirring rate is 200 rpm.
The thermoplastic polyolefin TPO and the nanoparticles are preferably mixed at 185 to 215 ℃ for 7.5 to 8.5min, more preferably at 200 ℃ for 8 min.
The invention provides an application of the low processing viscosity matte TPO skin material in the technical scheme or the low processing viscosity matte TPO skin material prepared by the preparation method in the technical scheme in an automotive interior material.
To further illustrate the present invention, the following examples are provided to describe in detail the low processing viscosity matte TPO skin material, its preparation method and its application, but they should not be construed as limiting the scope of the present invention.
Example 1
Step one, accurately weighing the raw materials of the components according to the formula of the following table 1
Table 1: raw material formulation of example 1
The ethylene propylene diene monomer has the ethylene propylene ratio of 80/20 and the Mooney viscosity ML1+ 432125 ℃, and has the characteristics of quick vulcanization, high tensile strength, low glass transition temperature, low permanent deformation and the like.
The polyolefin resin is an alpha-olefin copolymer, an olefin copolymer monomer, or a mixture thereof.
The melt index of the polypropylene is 20g/10min, and the alpha-olefin monomer in the polypropylene comprises: the radicals ethylene, 1-butene, 1-pentene and 1-hexene. The polypropylene has low volatility, high viscosity index, low pour point, high flash point, excellent high temperature oxidation performance, long service life, etc.
The polyolefin elastomer POE is a thermoplastic elastomer which adopts metallocene catalyst to realize in-situ polymerization of ethylene and octene, and has excellent toughness and good processability. The POE has no unsaturated double bond in the molecular structure, excellent ageing resistance, narrow molecular weight distribution, good flowability and good compatibility with polyolefin. The material has higher impact strength and elongation at break.
The low-density polyethylene has a melt index of 10g/10 min. The heat fusion property and the molding processability are good, the processing fluidity of the material can be increased, the flexibility is good, and the impact toughness, the low temperature resistance and the like of the material are improved.
The nanoparticles have a thickness of 1-3 nm, a diameter of 3-5 μm, 2-5 layers and a specific surface area of 500m2(ii) multilayer graphene per gram; the composite material has the characteristics of large specific surface area, outstanding mechanical property and excellent thermal property. Meanwhile, the ultra-high specific surface area, the surface roughness and the wrinkle characteristics can effectively reduce the glossiness of the material and improve the matte characteristic of the material.
And step two, setting the temperature of a HAAKE internal mixer to be 200 ℃, rotating at 200rpm, and adding the polyolefin resin, the low-density polyethylene, the ultraviolet light absorber, the antioxidant, the multilayer graphene, the carbon black, the polypropylene, the polyolefin elastomer and the ethylene propylene diene monomer in sequence for 8min to blend uniformly.
And step three, mixing the uniformly mixed mixture obtained in the step two on a double-roller plasticator, turning over for several times, and discharging after thinly passing.
And step four, hot pressing the blend for l5min at 180 ℃ by using a 25-ton flat vulcanizing machine, then cold pressing to room temperature to prepare a test piece with the thickness of 1mm, standing for 24h at room temperature, and cutting into a standard sample wafer with the diameter of 25mm for rheological experimental performance test.
And step five, using a DHR-2 type rheometer of American TA company, selecting a 25mm parallel plate at 160 ℃, performing dynamic frequency scanning on the sample obtained in the step four, wherein the testing frequency is 0.1rad/s-100rad/s, and in order to ensure that the rheological behavior is in a linear viscoelastic range, the tested strain amplitude is kept at 0.1% and the sample is preheated for 180s before the experiment.
TABLE 2 basic Properties of matte TPO skin from example 1
FIG. 1 is a graph showing the change in viscosity of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1; as can be seen from fig. 1: the addition of nanoparticles reduced the viscosity of the system of example 1 by up to 26% at different frequencies than comparative example 1. The above results show that the matte TPO skin obtained in example 1 can be subjected to kneading, calendering, extrusion, and other operations at lower temperatures than the TPO skin material of comparative example 1. The mixing temperature of the matt TPO skin obtained in example 1 is reduced from 210 ℃ to 200 ℃ compared with the TPO skin material in comparative example 1; the extrusion temperature is reduced from 200 ℃ to 190 ℃; the calendering temperature was reduced from 160 ℃ to 140 ℃.
FIG. 2 is a matte test chart of TPO skin materials prepared in examples 1-3 of the present invention and comparative example 1, and it can be seen from Table 2 that: the addition of the nanoparticles significantly reduced the gloss of the material of example 1 (comparative example 1 has a gloss of 4.5) and resulted in a matte surface.
Example 2
Step one, accurately weighing the raw materials of the components according to the formula shown in the following table 3
Table 3: raw material formulation of example 2
The thermoplastic rubber is thermoplastic dynamic fully vulcanized rubber (TPV), and the rubber has excellent tensile strength, high toughness and high rebound resilience; excellent environmental protection performance, repeated use and easy processing and forming; can be co-injected or extruded with PP, PA, PC, ABS, PS, PBT, PET and other materials.
The polyolefin resin is an alpha-olefin copolymer, an olefin copolymer monomer, or a mixture thereof.
The melt index of the polypropylene is 20g/10min, and the alpha-olefin monomer in the polypropylene comprises: the free radicals ethylene, 1-butene, 1-pentene, 1-hexene. Has low volatility, high viscosity index, low pour point, high flash point and excellent high temperature oxidation performance.
The polyolefin elastomer POE is a thermoplastic elastomer which adopts metallocene catalyst to realize in-situ polymerization of ethylene and octene, and has excellent toughness and good processability. The POE has no unsaturated double bond in the molecular structure, has excellent ageing resistance, narrow molecular weight distribution, better fluidity and good compatibility with polyolefin, and ensures that the material has higher impact strength and elongation at break.
The low-density polyethylene has a melt index of 10g/10 min. The heat fusion property and the molding processability are good, the processing fluidity of the material can be increased, the flexibility is good, and the impact toughness, the low temperature resistance and the like of the material are improved.
The nano particles are nano fumed silica, the particle size is 5-10nm, the particle size among the nano particles is smaller than the mean square gyration radius of the polymer, and the nano particles are uniformly distributed in the system, so that the viscosity reduction behavior of a high polymer system occurs. The refractive index of the fumed silica is 1.46, is close to that of the resin, can obviously reduce the surface gloss of the material, and is a good flatting agent.
And step two, setting the temperature of a HAAKE internal mixer to be 200 ℃, rotating at 200rpm for 8min, and sequentially adding polyolefin resin, low-density polyethylene, an ultraviolet light absorber, an antioxidant, fumed silica, carbon black, polypropylene, a polyolefin elastomer and thermoplastic rubber to be uniformly blended.
And step three, mixing the uniformly mixed mixture obtained in the step two on a double-roller plasticator, turning over for several times, and discharging after thinly passing.
And step four, hot pressing the blend for l5min at 180 ℃ by using a 25-ton flat vulcanizing machine, then cold pressing to room temperature to prepare a test piece with the thickness of 1mm, standing for 24h at room temperature, and cutting into a standard sample wafer with the diameter of 25mm for rheological experimental performance test.
And step five, using a DHR-2 type rheometer of American TA company, selecting a 25mm parallel plate at 160 ℃, performing dynamic frequency scanning on the sample obtained in the step four, wherein the testing frequency is 0.1rad/s-100rad/s, and in order to ensure that the rheological behavior is in a linear viscoelastic range, the tested strain amplitude is kept at 0.1% and the sample is preheated for 180s before the experiment.
TABLE 4 basic Properties of matte TPO skin from example 2
| Tensile strength, MPa | 19.2, reach the standard | GB/T 1040.3 |
| Elongation at break | 330% and reaches the standard | GB/T 1040.3 |
| Appearance of the product | Reach the standard | QC/T804-2008 |
| Degree of gloss | 2.5, reach the standard | QC/29089-2016 |
| Wear resistance | Grade 6, up to standard | GB/T 3920-2008 |
| Cold resistance | Reach the standard | QC/T804-2008 |
| VOC | Reach the standard | Q/FC-CD05-011-2014 |
| Smell(s) | C1, reach standard | QC/T804-2008 |
| Flame retardancy | 72mm/min, and reaches the standard | GB8410-2016 |
FIG. 1 is a graph showing the change in viscosity of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1; as can be seen from fig. 1: the addition of nanoparticles reduced the viscosity of the example 2 system by 39% at different frequencies than comparative example 1. The above results show that the matte TPO skin obtained in example 2 can be subjected to kneading, calendering, extrusion, and other operations at lower temperatures than the TPO skin material of comparative example 1. The mixing temperature of the matt TPO skin obtained in example 2 is reduced from 210 ℃ to 200 ℃ compared with the TPO skin material in comparative example 1; the extrusion temperature is reduced from 200 ℃ to 190 ℃; the calendering temperature was reduced from 160 ℃ to 140 ℃.
FIG. 2 is a matte test chart of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1, and it can be seen from Table 4 that: the addition of the nanoparticles significantly reduced the gloss of the material of example 2 (4.5 for comparative example 1) and resulted in a matte surface.
Example 3
Step one, accurately weighing the raw materials of the components according to the formula of the following table 5
Table 5: raw material formulation of example 3
The thermoplastic elastomer is a polyester type thermoplastic elastomer (TPU), and has the characteristics of high mechanical property, high impact strength, chemical resistance, oil resistance, radiation resistance, oxygen resistance, ozone resistance, excellent wear resistance and the like.
The polyolefin resin is an alpha-olefin copolymer, an olefin copolymer monomer, or a mixture thereof.
The melt index of the polypropylene is 20g/10min, and the alpha-olefin monomer in the polypropylene comprises: the free radicals ethylene, 1-butene, 1-pentene, 1-hexene. Has low volatility, high viscosity index, low pour point, high flash point and excellent high temperature oxidation performance.
The polyolefin elastomer is preferably a styrene/hexene-butene/styrene block copolymer (SEBS), and has good stability and aging resistance.
The low-density polyethylene has a melt index of 10g/10 min. The heat fusion property and the molding processability are good, the processing fluidity of the material can be increased, the flexibility is good, and the impact toughness, the low temperature resistance and the like of the material are improved.
The nano particles are 5-10nm monodisperse polystyrene microspheres. The addition of the nano-scale polystyrene microspheres can increase the free volume of polymer molecules, reduce the linear entanglement of the polymer and reduce the melt viscosity of the system, thereby reducing the macroscopic viscosity of the system.
And step two, self-preparing monodisperse polystyrene microspheres. 100ml of water, 15ml of a hydrophobic monomer styrene, from Luborun
2700 dispersant and 0.05g of sodium bicarbonate as pH regulator were added to a three-necked flask equipped with stirring device, reflux device and N2A conduit. Stirring at the speed of 300 revolutions per minute for 30 minutes at room temperature, introducing nitrogen, evacuating the air in the system, heating to 70 ℃, adding a certain amount of initiator potassium persulfate, and reacting for 3 hours to obtain polystyrene emulsion; drying to obtain the monodisperse nano-scale polystyrene microsphere.
Setting the temperature of a HAAKE internal mixer to 200 ℃, rotating speed of 200rpm, and time of 8min, sequentially adding the thermoplastic elastomer, the low-density polyethylene, the ultraviolet absorber, the antioxidant, the nano-scale polystyrene microspheres, the carbon black, the polypropylene, the polyolefin elastomer and the ethylene propylene diene monomer, and uniformly blending.
And step four, mixing the uniformly mixed mixture obtained in the step three on a double-roller plasticator to mix the sizing material, turning over for several times, and discharging after thinly passing.
And fifthly, hot pressing the blend for l5min at 180 ℃ by using a 25-ton flat vulcanizing machine, then cold pressing to room temperature to prepare a test piece with the thickness of 1mm, standing for 24h at room temperature, and cutting the test piece into a standard sample wafer with the diameter of 25mm for rheological experimental performance test.
And step six, using a DHR-2 type rheometer of American TA company, selecting a 25mm parallel plate at 160 ℃, performing dynamic frequency scanning on the sample obtained in the step five, wherein the testing frequency is 0.1rad/s-100rad/s, and in order to ensure that the rheological behavior is in a linear viscoelastic range, the tested strain amplitude is kept at 0.1% and the sample is preheated for 180s before the experiment.
TABLE 6 basic Properties of matte TPO skin from example 3
FIG. 1 is a graph showing the change in viscosity of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1; as can be seen from fig. 1: the addition of nanoparticles reduced the viscosity of the system of example 3 by up to 44% at different frequencies than comparative example 1. The above results show that the matte TPO skin obtained in example 3 can be subjected to kneading, calendering, extrusion, and other operations at lower temperatures than the TPO skin material of comparative example 1. The mixing temperature of the matt TPO skin obtained in example 3 is reduced from 210 ℃ to 190 ℃ compared with the TPO skin material in comparative example 1; the extrusion temperature is reduced from 200 ℃ to 180 ℃; the calendering temperature was reduced from 160 ℃ to 130 ℃.
FIG. 2 is a matte test chart of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1, and it can be seen from Table 6 that: the addition of the nanoparticles significantly reduced the gloss of the material of example 3 (comparative example 1 has a gloss of 4.5) and resulted in a matte surface.
Comparative example 1
Step one, accurately weighing the raw materials of the components according to the formula shown in the following table 7
Table 7 raw material formulation of comparative example 1
And step two, setting the temperature of a HAAKE internal mixer to 210 ℃, rotating the HAAKE internal mixer at the speed of 200rpm for 8min, and sequentially adding polyolefin resin, low-density polyethylene, an ultraviolet light absorber, an antioxidant, polypropylene, a polyolefin elastomer and ethylene propylene diene monomer rubber to be uniformly blended.
And step three, mixing the uniformly mixed mixture obtained in the step two on a double-roller plasticator, turning over for several times, and discharging after thinly passing.
And step four, hot pressing the blend for l5min at 180 ℃ by using a 25-ton flat vulcanizing machine, then cold pressing to room temperature to prepare a test piece with the thickness of 1mm, standing for 24h at room temperature, and cutting into a standard sample wafer with the diameter of 25mm for rheological experimental performance test.
And step five, using a DHR-2 type rheometer of American TA company, selecting a 25mm parallel plate at 160 ℃, performing dynamic frequency scanning on the sample obtained in the step four, wherein the testing frequency is 0.1rad/s-100rad/s, and in order to ensure that the rheological behavior is in a linear viscoelastic range, the tested strain amplitude is kept at 0.1% and the sample is preheated for 180s before the experiment.
TABLE 8 basic Properties of TPO skin obtained in comparative example 1
| Tensile strength, MPa | 15.5, reach the standard | GB/T 1040.3 |
| Elongation at break | 490 percent and reaches the standard | GB/T 1040.3 |
| Appearance of the product | Reach the standard | QC/T804-2008 |
| Degree of gloss | 4.5, not reaching the standard | QC/29089-2016 |
| Wear resistance | Grade 3, not reaching the standard | GB/T 3920-2008 |
| Cold resistance | Reach the standard | QC/T804-2008 |
| VOC | Reach the standard | Q/FC-CD05-011-2014 |
| Smell(s) | C1, reach standard | QC/T804-2008 |
| Flame retardancy | 82mm/min, up to the standard | GB8410-2016 |
FIG. 1 is a graph showing the change in viscosity of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1; as can be seen from fig. 1: comparative example 1 has the highest viscosity. The mixing temperature of the TPO skin material in the comparative example 1 is 210 ℃, the extrusion temperature is 200 ℃, and the rolling temperature is 160 ℃ and is reduced to 130 ℃, which are higher than the operation temperature in the examples 1 to 3.
FIG. 2 is a matte test chart of TPO skin materials prepared in examples 1 to 3 of the present invention and comparative example 1, and it can be seen from Table 8 that: the gloss of comparative example 1 was 4.5 and did not meet the standards, and the abrasion resistance was also not met, while both of examples 1-3 were met.
The embodiments show that the invention provides a low processing viscosity matte TPO skin material, which comprises the following components in a mass ratio of 90-99.5: 0.5-10 parts of thermoplastic polyolefin TPO and nano particles; the nano particles are selected from one or more of multi-layer graphene, carbon nano tubes, monodisperse polystyrene microspheres, manganese oxide nano wires, ferroferric oxide nano particles, gas-phase silica and nano carbon black particles. The invention adopts the nano particles to be filled in the thermoplastic polyolefin TPO, increases the free volume of the polymer, reduces the entanglement density, simultaneously generates interface slippage between the nano particles and macromolecules, and is equivalent to the action of a lubricant to reduce the viscosity of a system, thereby reducing the process temperature of operations such as mixing, calendering, extruding and the like in the material processing process and fundamentally solving a series of problems caused by overhigh material temperature in the industrial production process. The nano particles also have the extinction effect, reduce the glossiness of the material and make the surface of the material matte; the addition of the nano particles has little influence on the mechanical properties of the material, improves the wear resistance coefficient and provides a guiding significance for industrial production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A low processing viscosity TPO skin material that dumb, includes the mass ratio and is 90 ~ 99.5: 0.5-10 parts of thermoplastic polyolefin TPO and nano particles;
the nano particles are selected from one or more of multi-layer graphene, carbon nano tubes, monodisperse polystyrene microspheres, manganese oxide nano wires, ferroferric oxide nano particles, gas-phase silica and nano carbon black particles.
2. The TPO skin material according to claim 1, wherein the multi-layer graphene has a thickness of 1 to 3nm, a diameter of 3 to 5 μm, 2 to 5 layers, and a specific surface area of 480 to 520m2/g；
The diameter of the carbon nano tube is 6-8 nm, and the length of the carbon nano tube is 48-52 mu m;
the diameter of the monodisperse polystyrene microsphere is 5-10 nm;
the diameter of the manganese oxide nanowire is 9-11 nm;
the particle size of the ferroferric oxide nano particles is 9-11 nm;
the particle size of the fumed silica is 5-10 nm;
the particle size of the nano carbon black particles is 5-10 nm.
3. The TPO skin material according to claim 1, wherein the thermoplastic polyolefin TPO comprises the following components in a mass ratio of 30 to 60: 1-40: 1-30: 0.1-1: 0.05-5: 0.1-3 of rubber, polyolefin resin, elastomer, ultraviolet absorber, antioxidant, carbon black and flame retardant.
4. The TPO skin material of claim 3, in which the rubber is selected from one or more of ethylene propylene rubber, ethylene propylene diene monomer rubber, styrene butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, thermoplastic dynamic fully vulcanized rubber, polyurethane elastomers and fluororubbers;
the polyolefin resin is selected from one or more of polyethylene, polypropylene, polyisobutylene, poly 4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer;
the elastomer is selected from ethylene elastomers and/or styrene elastomers.
5. The TPO skin material of claim 4, wherein the polypropylene has a melt index of 20g/10 min; the polyethylene is selected from low density polyethylene with a melt index of 10g/10 min.
6. The TPO skin material of claim 4, wherein the ethylene-based elastomer is selected from one or more of ethylene/octene copolymers, olefin block copolymers, ethylene/propylene copolymers and ethylene/propylene/butadiene copolymers;
the styrene elastomer is selected from one or more of styrene/butadiene/styrene block copolymer, hydrogenated styrene/butadiene/styrene block copolymer, styrene/isoprene/styrene block copolymer, styrene/hexene-butene/styrene block copolymer and styrene/ethylene-propylene/styrene block copolymer.
7. The TPO skin material of claim 3, wherein the rubber is selected from one or more of ethylene propylene diene monomer rubber type FG1901, thermoplastic dynamically fully vulcanized rubber type 251-70W232, and polyurethane elastomer type 385E;
the polyolefin resin is selected from one or more of polyolefin resin type 101-73, polypropylene type 1120, and low density polyethylene type 5021 DX;
the elastomer is selected from styrene/hexene-butene/styrene block copolymers of type G1650M and/or ethylene/octene copolymers of type LG LC 175.
8. The TPO skin material of claim 3, in which the ultraviolet light absorber comprises bis (1,2,2,6, 6-pentamethyl-4 piperidinyl) sebacate and/or poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidinyl) succinate;
the antioxidant comprises tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid ] pentaerythritol ester antioxidant and/or octadecyl 3, 5-di-tert-butyl-4-hydroxyphenyl propionate antioxidant;
the model of the carbon black is MCF-88;
the flame retardant is selected from triphenyl phosphate.
9. A method for preparing the TPO skin material according to any one of claims 1 to 8, comprising the steps of:
and (2) mixing the components in a mass ratio of 90-99.5: and (3) mixing 0.5-10 of thermoplastic polyolefin TPO and the nano particles at 180-230 ℃ for 7-9 min to obtain the low-processing-viscosity matte TPO skin material.
10. Use of the low processing viscosity matte TPO skin material according to any one of claims 1 to 8 or the low processing viscosity matte TPO skin material prepared by the preparation method according to claim 9 in an automotive interior material.
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