CN101698726A - Scratch-resistant modified polypropylene composite material and preparation method thereof - Google Patents
Scratch-resistant modified polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of modified polypropylene composite materials and relates to a scratch-resistant modified polypropylene composite material which is applicable to manufacturing automotive interior parts and comprises the following components by parts by weight: 60-90 parts of polypropylene, 5-20 parts of plasticizer, 5-20 parts of mineral filler, 0.1-4 parts of wear-resistant agent/scratch-resistant agents and 0.1-3 parts of additives, wherein the wear-resistant agent/scratch-resistant agents can be selected from the mixture of nano-polytetrafluoroethylene superfine micro-powder, organic matter-modified siloxane, modified silicone mixture and reactive modified polysiloxane. The prepared modified polypropylene composite material has high surface gloss and better impact-resistant performance, strength, melt fluidity and mechanical performance; furthermore, due to the use of the various wear-resistant agents/scratch-resistant agents, the scratch-resistant performance of the product is excellent; and the resources of the required raw materials are simultaneously extensive and easy to obtain.
Description
Technical field
The invention belongs to field of modified polypropylene composite materials, be specifically related to a kind of anti-wear agent/scratch resistance liniment modified polypropylene composite material, relate in particular to a kind of modified polypropylene composite material that is applicable to the scrape resistant of making automotive upholstery; The present invention also relates to the preparation method of described modified polypropylene composite material simultaneously.
Background technology
With respect to engineering plastics, polyolefine materials such as polypropylene, toughening agent modified polypropylene, TPO and thermoplastic elastomer have the advantage recyclable, in light weight, that cost is low, thereby are applied to automobile and other field more and more.Yet the scraping and wiping resistance performance of polyolefine material is obviously relatively poor, and this performance is the key property of automotive interior application parts such as dashboard, operation bench and door-plate epidermis.Scrath resistance is one of key property of automobile external application component, ATVs vehicles such as (all-terrain vehicles), dutiable goods and furniture etc.Plastics and automotive industry are just actively sought solution to improve the scraping and wiping resistance performance of polyolefine material.
The main terms of settlement that improves scraping and wiping resistance performance is exactly to improve the surface hardness of material, the report of relevant raising polypropylene scraping and wiping resistance performance has had much at present, mainly is by adding functional aid,, and other polymer blendings 3 kind methods compound with mineral filler.For example:
1, publication number is that the Chinese invention patent of 101255253A (application number is 200810023328.X) discloses a kind of scraping-resistant automobile inner fitting special-purpose material and preparation method thereof, this PP Pipe Compound is prepared from by following constituent mass part: 80～90 parts of polypropylene, 10～20 parts of superfine talcum powders, 1.0～3.0 parts of low molecule organic matter expellents, 1.0～2.0 parts in oxidation inhibitor, its preparation method comprises the steps: 1) polypropylene and lubricant, oxidation inhibitor were mixed under 300～500 rev/mins rotating speed 3～5 minutes; 2) adding superfine talcum powder mixed under 300～500 rev/mins rotating speed 5～10 minutes; 3) under 1500～2000 rev/mins rotating speed, mixed 10～15 minutes; 4) under 300～500 rev/mins rotating speed, mixed 5～10 minutes, obtain Preblend; 5) Preblend is got product through three grades of vacuum extruding pelletizations of forcing machine.
2, U.S. Pat 5585420 and US5731376 have proposed the anti-scratch performance that a kind of method that adds organo-siloxane improves talc powder filled polypropylene, but not mentioned rubber toughened.
Summary of the invention
The object of the invention provides a kind of modified polypropylene composite material of scrape resistant.
For achieving the above object, the technical solution used in the present invention is: a kind of modified polypropylene composite material of scrape resistant comprises: polypropylene, toughner, mineral filler, anti-wear agent/scratch resistance liniment and auxiliary agent, and according to weight part, the weight part of above-mentioned composition is respectively:
Polypropylene 60-90;
Toughner 5-20;
Mineral filler 5-20;
Anti-wear agent/scratch resistance liniment 0.1-4;
Auxiliary agent 0.1-3;
Wherein, the weight part sum of polypropylene, toughner and mineral filler is 100 parts.
In the technique scheme, described polypropylene, toughner, mineral filler, anti-wear agent/scratch resistance liniment or auxiliary agent all are to well known to a person skilled in the art composition commonly used, particularly:
Described polypropylene is selected from: the mixture of one or both in high crystalline homo-polypropylene or the Co-polypropylene.Wherein, the molecular weight ranges of homo-polypropylene is 30～400,000; The mol ratio of propylene monomer and vinyl monomer is 13: 7～17: 3 in the Co-polypropylene; Its degree of crystallinity must not be lower than 70%.
Described toughner is selected from: the mixture of one or more in ethylene-octene copolymer (POE), ethylene-butene copolymer, the ethylene-propylene copolymer.
Described mineral condiment is selected from: the mixture of one or more in talcum powder, lime carbonate, wollastonite, glass microballon or the glass fibre.Wherein, the talcum powder particle diameter is 1500～3000 orders; The lime carbonate particle diameter is 800～2500 orders; The wollastonite particle diameter is 6～12 μ m; The glass microballon particle diameter is 15～135 μ m; Glass fiber diameter is 7～30 μ m.
Described auxiliary agent is selected from: the mixture of one or more among antioxidant 1010, oxidation inhibitor 619, oxidation inhibitor 168, antioxidant 1076, oxidation inhibitor PS802, photostabilizer 770, photostabilizer 944, photostabilizer UV-3853 or the uv-absorbing agent UV-2908;
Be for the CAS of antioxidant 1010 number: 6683-19-8, molecular formula is: C
73H
108O
12, chemistry is by name: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
The chemistry of oxidation inhibitor 619 is by name: distearyl pentaerythrityl diphosphite;
Be for the CAS of oxidation inhibitor No. 168: 31570-04-4, molecular formula is: C
42H
63O
3P, chemistry is by name: tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
Be for the CAS of antioxidant 1076 number: 2082-79-3, molecular formula is: C
35H
62O
3, chemistry is by name: β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid;
Be for the CAS of oxidation inhibitor PS802 number: 693-36-7, molecular formula is: C
42H
82O
4S, chemistry is by name: thio-2 acid 2 stearyl ester, chemistry is by name: thio-2 acid 2 stearyl ester;
Be for the CAS of photostabilizer No. 770: 52829-07-9, molecular formula is: C
28H
52O
4N
2, chemistry is by name: two (2,2,6,6-tetramethyl--4-piperidyl) sebate;
Be for the CAS of photostabilizer No. 944: 70624-18-9, molecular formula is: (C
35H
66N
8) n=
4-5, chemistry is by name: poly-[6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-[(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1, oneself two supports [(2,2,6,6-tetramethyl--4-piperidyl) imino-] of 6-};
Be for the CAS of photostabilizer UV-3853 number: 167078-06-0, molecular formula is: C
27H
53NO
2, chemistry is by name: 2,2,6, and 6-tetramethyl--4-piperidines stearate;
Be for the CAS of uv-absorbing agent UV-2908 number: 67845-93-63, molecular formula is: C
31H
54O
3, chemistry is by name: 5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester.
The preparation method of the modified polypropylene composite material of above-mentioned scrape resistant may further comprise the steps:
(1) takes by weighing raw material by above-mentioned weight proportion;
(2) with polypropylene and toughner 1000～2000 rev/mins of following high-speed mixing 5～20 minutes; Add mineral filler then, 1000～2000 rev/mins of following high-speed mixing 5～20 minutes; Add anti-wear agent/scratch resistance liniment and other auxiliary agents again,, obtain Preblend 1000～2000 rev/mins of following high-speed mixing 5～10 minutes;
(3) Preblend is fed in the twin screw extruder, preheat 3～5 minutes, wherein the temperature in each district of screw rod is 190～250 ℃, and screw speed is 200～500 rev/mins, and extruding pelletization can make the modified polypropylene composite material of scrape resistant.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the obtained modified polypropylene composite material surface gloss of the present invention height not only has impact resistance and intensity preferably, fluidity of molten, and owing to use.
2. not only scraping and wiping resistance performance is good for the obtained modified polypropylene composite material of the present invention, but also has excellent mechanical property, and required starting material wide material sources conveniently are easy to get simultaneously.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
Get the raw materials ready by following prescription:
(a) polypropylene 70 mass parts
(b) toughner 10 mass parts (POE)
(c) mineral filler 20 mass parts (talcum powder)
(d) anti-wear agent/scratch resistance liniment 7 mass parts
(e) other auxiliary agent 1 mass parts
Wherein, anti-wear agent/scratch resistance liniment comprises: but nano level tetrafluoroethylene ultra-fine micropowder, organism modified siloxane, modified silicone mixture response type modified polyorganosiloxane, according to mass ratio, nano level tetrafluoroethylene ultra-fine micropowder: organism modified siloxane: modified silicone mixture: but the response type modified polyorganosiloxane=5: 0.4: 0.6: 1;
Earlier polypropylene and toughner are mixed under 1200 rev/mins rotating speed and stirred 5 minutes, add mineral filler then, under 1500 rev/mins rotating speed, stirred 10 minutes, add anti-wear agent/scratch resistance liniment and auxiliary agent at last again, under 1200 rev/mins rotating speed, stirred 5 minutes, obtain Preblend.In this Preblend feeding twin screw extruder, extruding pelletization obtains scratch-resistant modified polypropylene composite material, can be used for automotive upholstery.
After testing, the polypropylene compound material prepared performance is as follows:
Density 1.07g/cm
3
Scraping DL=1.62
Tensile strength 21.8MPa
Flexural strength 43.3MPa
Modulus in flexure 2.37GPa
Notched Izod impact strength 17.2KJ/m
2
Ball indentation hardness 57.5N/mm
2
96.1 ℃ of heat-drawn wires
Embodiment two
Get the raw materials ready by following prescription:
(a) polypropylene 70 mass parts
(b) toughner 10 mass parts (POE)
(c) mineral filler 20 mass parts
(d) anti-wear agent/scrape resistant auxiliary agent 7 mass parts
(e) other auxiliary agent 1 mass parts
Wherein, mineral filler comprises: talcum powder and lime carbonate, and according to mass ratio, talcum powder: lime carbonate=1: 1; Anti-wear agent/scratch resistance liniment comprises: but nano level tetrafluoroethylene ultra-fine micropowder, organism modified siloxane, modified silicone mixture response type modified polyorganosiloxane, according to mass ratio, nano level tetrafluoroethylene ultra-fine micropowder: organism modified siloxane: modified silicone mixture: but the response type modified polyorganosiloxane=5: 0.4: 0.8: 0.8;
Earlier polypropylene and mineral filler are mixed under 1200 rev/mins rotating speed and stirred 5 minutes, add the odor adsorption agent then, under 1500 rev/mins rotating speed, stirred 10 minutes, add auxiliary agent at last again, under 1200 rev/mins rotating speed, stirred 5 minutes, obtain Preblend.In this Preblend feeding twin screw extruder, extruding pelletization obtains scratch-resistant modified polypropylene composite material, can be used for automotive upholstery.
After testing, the polypropylene compound material prepared performance is as follows:
Density 1.07g/cm
3
Scraping DL=1.16
Tensile strength 24.5MPa
Flexural strength 39.7MPa
Modulus in flexure 2.16GPa
Notched Izod impact strength 16.7KJ/m
2
Ball indentation hardness 63.0N/mm
2
97.4 ℃ of heat-drawn wires
Embodiment three
Get the raw materials ready by following prescription:
(a) polypropylene 70 mass parts
(b) toughner 10 mass parts (POE)
(c) mineral filler 20 mass parts
(d) anti-wear agent/scrape resistant auxiliary agent 7 mass parts
(e) other auxiliary agent 1 mass parts
Wherein, mineral filler comprises: talcum powder and lime carbonate, and according to mass ratio, talcum powder: lime carbonate=1: 1; Anti-wear agent/scratch resistance liniment comprises: but nano level tetrafluoroethylene ultra-fine micropowder, organism modified siloxane, modified silicone mixture response type modified polyorganosiloxane, according to mass ratio, nano level tetrafluoroethylene ultra-fine micropowder: organism modified siloxane: modified silicone mixture: but the response type modified polyorganosiloxane=5: 0.4: 1: 0.6;
Earlier polypropylene and toughner are mixed under 1200 rev/mins rotating speed and stirred 5 minutes, add mineral filler then, under 1500 rev/mins rotating speed, stirred 10 minutes, add anti-wear agent/scratch resistance liniment and auxiliary agent at last again, under 1200 rev/mins rotating speed, stirred 5 minutes, obtain Preblend.In this Preblend feeding twin screw extruder, extruding pelletization obtains scratch-resistant modified polypropylene composite material, can be used for automotive upholstery.
After testing, the polypropylene compound material prepared performance is as follows:
Density 1.07g/cm
3
Scraping DL=0.52
Tensile strength 24.8MPa
Flexural strength 40.1MPa
Modulus in flexure 2.21GPa
Notched Izod impact strength 18KJ/m
2
Ball indentation hardness 63.8N/mm
2
97.3 ℃ of heat-drawn wires
Embodiment four
Get the raw materials ready by following prescription:
(a) polypropylene 70 mass parts
(b) toughner 10 mass parts (POE)
(c) mineral filler 20 mass parts
(d) anti-wear agent/scrape resistant auxiliary agent 7 mass parts
(e) other auxiliary agent 1 mass parts
Wherein, mineral filler comprises: talcum powder and lime carbonate, and according to mass ratio, talcum powder: lime carbonate=1: 1; Anti-wear agent/scratch resistance liniment comprises: but nano level tetrafluoroethylene ultra-fine micropowder, organism modified siloxane, modified silicone mixture response type modified polyorganosiloxane, according to mass ratio, nano level tetrafluoroethylene ultra-fine micropowder: organism modified siloxane: modified silicone mixture: but the response type modified polyorganosiloxane=5: 0.6: 1: 0.4;
Earlier polypropylene and toughner are mixed under 1200 rev/mins rotating speed and stirred 5 minutes, add mineral filler then, under 1500 rev/mins rotating speed, stirred 10 minutes, add anti-wear agent/scratch resistance liniment and auxiliary agent at last again, under 1200 rev/mins rotating speed, stirred 5 minutes, obtain Preblend.In this Preblend feeding twin screw extruder, extruding pelletization obtains scratch-resistant modified polypropylene composite material, can be used for automotive upholstery.
After testing, the polypropylene compound material prepared performance is as follows:
Density 1.06g/cm
3
Scraping DL=1.21
Tensile strength 24.9MPa
Flexural strength 41.2MPa
Modulus in flexure 2.28GPa
Notched Izod impact strength 16.8KJ/m
2
Ball indentation hardness 64.3N/mm
2
96.8 ℃ of heat-drawn wires
These embodiment only are used to the present invention is described and should not limit the scope of this invention.In addition, after having read content of the present invention, those skilled in the art make the change or the modification of the various equivalent form of values to the present invention, and these equivalent form of values belong to claims institute restricted portion of the application equally.
Claims (9)
1. the modified polypropylene composite material of a scrape resistant, comprising: polypropylene, toughner, mineral filler, anti-wear agent/scratch resistance liniment and auxiliary agent is characterized in that according to weight part, the weight part of above-mentioned composition is respectively:
Polypropylene 60-90;
Toughner 5-20;
Mineral filler 5-20;
Anti-wear agent/scratch resistance liniment 0.1-4;
Auxiliary agent 0.1-3;
Wherein, the weight part sum of polypropylene, toughner and mineral filler is 100 parts.Described anti-wear agent/scratch resistance liniment is selected from: but the mixture of four kinds of nano level tetrafluoroethylene ultra-fine micropowders, organism modified siloxane, modified silicone mixture response type modified polyorganosiloxane.
2. according to the modified polypropylene composite material of the described scrape resistant of claim 1, it is characterized in that: but the weight ratio of nano level tetrafluoroethylene ultra-fine micropowder, organism modified siloxane, modified silicone mixture response type modified polyorganosiloxane is 5: 0.4: 1: 0.6.
3. according to the modified polypropylene composite material of the described scrape resistant of claim 1, it is characterized in that: described polypropylene is selected from: high crystalline homo-polypropylene or block copolymerization polypropylene can be single, also can be blended; Its degree of crystallinity must not be lower than 70%.
4. according to the modified polypropylene composite material of the described scrape resistant of claim 1, it is characterized in that: described toughner is selected from: the mixture of one or more in ethylene-octene copolymer (POE), ethylene-butene copolymer, the ethylene-propylene copolymer.
5. according to the modified polypropylene composite material of the described scrape resistant of claim 1, it is characterized in that: described mineral condiment is selected from: the mixture of one or more in talcum powder, lime carbonate, wollastonite, glass microballon or the glass fibre.
6. according to the modified polypropylene composite material of the described scrape resistant of claim 1, it is characterized in that: described anti-wear agent is selected from: nano level tetrafluoroethylene ultra-fine micropowder.
7. according to the modified polypropylene composite material of the described scrape resistant of claim 1, it is characterized in that: described scratch resistance liniment is selected from: but the mixture of three kinds of organism modified siloxanes, modified silicone mixture response type modified polyorganosiloxane.
8. according to the modified polypropylene composite material of the described scrape resistant of claim 1, it is characterized in that: described auxiliary agent is selected from: the mixture of one or more among antioxidant 1010, oxidation inhibitor 619, oxidation inhibitor 168, antioxidant 1076, oxidation inhibitor PS802, photostabilizer 770, photostabilizer 944, photostabilizer UV-3853 or the uv-absorbing agent UV-2908.
9. the preparation method of the modified polypropylene composite material of a scrape resistant is characterized in that: may further comprise the steps:
(1) takes by weighing raw material by the described weight proportion of claim 1;
(2) with polypropylene and toughner 1000～2000 rev/mins of following high-speed mixing 5～20 minutes; Add mineral filler then, 1000～2000 rev/mins of following high-speed mixing 5～20 minutes; Add anti-wear agent/scratch resistance liniment and other auxiliary agents again,, obtain Preblend 1000～2000 rev/mins of following high-speed mixing 5～10 minutes;
(3) Preblend is fed in the twin screw extruder, preheat 3～5 minutes, wherein the temperature in each district of screw rod is 190～250 ℃, and screw speed is 200～500 rev/mins, and extruding pelletization can make the modified polypropylene composite material of scrape resistant.
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-
2009
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