CN109912884A - A kind of wear-resisting scratch-resistant PP composite material of high glaze and its preparation method and application - Google Patents
A kind of wear-resisting scratch-resistant PP composite material of high glaze and its preparation method and application Download PDFInfo
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- CN109912884A CN109912884A CN201910118934.8A CN201910118934A CN109912884A CN 109912884 A CN109912884 A CN 109912884A CN 201910118934 A CN201910118934 A CN 201910118934A CN 109912884 A CN109912884 A CN 109912884A
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- silane coupling
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Abstract
The present invention relates to wear-resisting scratch-resistant PP composite materials of a kind of high glaze and its preparation method and application.Primary raw material composition are as follows: polypropylene, silicon rubber-silane coupling agent-hollow glass micropearl reactant, filler and auxiliary agent packet.In the wear-resisting scratch-resistant PP composite material of high glaze prepared by the present invention, polyacrylic narrow molecular weight distribution, hollow glass micropearl and silicon rubber are mainly distributed on the surface layer of material, article surface glossiness is high, processability is good, shrinking percentage is low, and Injection moulded part is not likely to produce current mark, and alternative ABS etc. is for products more demanding to gloss, wear-resisting scraping and wiping resistance performance such as appliance shell, automotive trim strip, door handles.
Description
Technical field
The invention belongs to High Polymer Material & Porcessing fields, and in particular to a kind of wear-resisting scratch-resistant polypropylene composite materials of high glaze
Material and its preparation method and application.
Background technique
Polypropylene (PP) is as one of general-purpose plastics, with nontoxic, cheap, relative density is small, resistant to chemical etching, strong
The advantages that spending height, being easily recycled, is widely used in the fields such as household electrical appliance, auto parts and components, articles for daily use.
High-gloss polypropylene is widely used in appliance shell as alternative ABS of the higher material of glossiness etc., day is commonly used
Product shell, automotive trim strip etc., but compared with ABS, polypropylene is there are wear-resisting scratch resistance is poor, the especially poor meeting of wearability
Making polypropylene material, glossiness constantly reduces in use, and this greatly limits polyacrylic application fields.It is high at present
Gloss polypropylene mainly by using high-gloss polypropylene, and be added on glossiness influence lesser filler such as glass microballoon,
Barium sulfate, calcium carbonate etc., deficiency is, one side high-gloss polypropylene price is higher, on the other hand wear-resisting scraping and wiping resistance performance
It cannot be improved.
Patent CN102206377A discloses a kind of high gloss formable polypropylene composite material and preparation method thereof, composition
For bimodal volcanic rocks, polypropylene, elastomer, filling modifying agent, heat stabilizer, nucleating agent and processing aid, house can be applied to
Electric shell etc..
Patent CN103694562A discloses a kind of automotive upholstery with exempting to spray scratch-resistant PP composite material, by gathering
Propylene, elastomer, talcum powder, compatilizer, metallic pigments, metal pigment surfaces inorganic agent, scratch resistance liniment, antioxidant and light are stablized
The composite material of agent composition, preparation has metal color, and has certain scraping and wiping resistance performance.
Patent CN107141609A discloses a kind of scratch-resistant PP composite material and preparation method thereof, with polypropylene and
Thermoplastic polyester elastomer is main comprise material, and thermoplastic polyester elastomer can float on polyacrylic surface and form a kind of densification
Protective film, thus make PP composite material have good scraping and wiping resistance performance.
Patent CN106589584A discloses a kind of lightweight, scratch-resistant, high luster materials and preparation method thereof and is making
Application in standby automobile interior decoration instrument board, uses the homopolypropylene of high rigidity, and high-intensitive, high heat resistance high melt body intensity is poly-
Propylene and nucleating agent and a small amount of nano inorganic powder are compound, form one layer of bright macromolecule membrane, enhancing in instrument panel surface
The scraping and wiping resistance performance and glossiness of instrument board.
Above-mentioned patent not can solve polyacrylic wear-resisting scratch-resistant problem, and especially bloom is polyacrylic wear-resisting resistance to
Scraping problem needs to develop new product and matched processing technology, to make up the deficiencies in the prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of wear-resisting scratch-resistant PP composite materials of high glaze.The material use isocyanide
Acid esters is reacted with hydroxyl introduces silane coupling agent at silicon rubber both ends, then passes through silane coupling agent and hollow glass micropearl surface water
Reaction, so that hollow glass micropearl is bound up on the both ends of silicon rubber；Meanwhile silicon rubber and polyacrylic compatibility are poor, are infusing
Silicon rubber can be with hollow glass micropearl together to the surface migration of material, to make hollow glass micropearl master in modeling process
It is distributed in the surface layer of product, realizes the effect of wear-resisting scratch-resistant.Influence of the hollow glass micropearl on surface layer to glossiness is reduced
It is small, and it is relatively fewer on surface layer to be uniformly distributed event in the material to the filler that glossiness is affected, to keep product again fine
Ground maintains glossiness.
Another object of the present invention is to provide the preparation methods of the wear-resisting scratch-resistant PP composite material of the high glaze.It should
Method prepares silicon rubber-silane coupling agent-hollow glass micropearl reactant first, and introduces peroxide and nucleating agent rush
It is migrated during fabricated product toward surface layer into silicon rubber-silane coupling agent-hollow glass micropearl reactant, to be conducive to
Obtain the PP composite material product of high gloss, wear-resisting scratch-resistant.
Another object of the present invention is to provide the wear-resisting scratch-resistant PP composite material of the high glaze in processing high glaze
Purposes in the high molecular material product of wear-resisting scratch-resistant.
To realize the above goal of the invention and reaching above-mentioned technical effect, technical scheme is as follows:
A kind of wear-resisting scratch-resistant PP composite material of high glaze, is prepared by following component:
S1, polypropylene, 60%~90%, preferably 65%~85%；
S2, silicon rubber-silane coupling agent-hollow glass micropearl reactant, 2%~20%, preferably 5%~10%；
S3, filler, 5~30%, preferably 10~20%；
S4, auxiliary agent packet, contain lubricant 0.01%~2%, preferably 0.2%~1%, peroxide 0.001%~0.2%,
It is preferred that 0.01%~0.1%, antioxidant 0.1%~2%, preferably 0.2%~1%, nucleating agent 0.01%~2%, preferably 0.2%
~1%；
The ratio of the above component is based on PP composite material gross mass.
In the present invention, the polypropylene that S1 is selected is homopolypropylene and/or copolymer polypropylene, and melting means range is 1-60g/
10min, preferably melting means range are 3-30g/10min.
In the present invention, S2 is prepared by following component:
S2-1, hollow glass micropearl；
S2-2, hydroxy-terminated silicone rubbre react to obtain silicon rubber-silane coupling agent reactant with silane coupling agent, reaction
Object dosage is the 5%~30% of hollow glass micropearl quality, preferably 10%~20%；
S2-3, silane coupling agent, silane coupling agent dosage are the 0.5%~5% of hydroxy-terminated silicone rubbre quality, preferably 1%
~3%；
Organic solvent need to be added when preparing S2, organic solvent is preferably tetrahydrofuran, and organic solvent and silicon rubber-silane are even
The mass ratio for joining agent reactant is (2~10): 1, preferably (4~6): 1.
In the present invention, the hollow glass micropearl diameter that S2-1 is selected is 1~100 μm, preferably 2~50 μm；What S2-2 was selected
Hydroxy-terminated silicone rubbre molecular weight is 10,000~150,000, preferably 15,000~50,000；S2-3 select silane coupling agent beGlycidyl ether oxygen propyl trimethoxy silicane (such as KH560), 3- isocyanatopropyl triethoxysilane (such as ALINK-
25) and one of 3- isocyanatopropyl trimethoxy silane (such as ALINK-35) or a variety of, preferred 3- isocyanatopropyl three
Ethoxysilane (such as ALINK-25) and/or 3- isocyanatopropyl trimethoxy silane (such as ALINK-35).
In the present invention, the filler that S3 is selected is one of barium sulfate, calcium carbonate and talcum powder or a variety of.
In the present invention, the lubricant in S4 auxiliary agent packet is calcium stearate, zinc stearate, magnesium stearate, white oil and paraffin oil
One of or it is a variety of；Peroxide is cumyl peroxide (DCP), benzoyl peroxide (BPO), two-(t-butyl peroxies
Change isopropyl) one of benzene (tasteless DCP) and di-tert-butyl peroxide (DTBP) or a variety of；Antioxidant be 1010,1076,
One of 168 and 626 or a variety of；Nucleating agent is NA11 and/or NA21.
In the present invention, the preparation method of the PP composite material is comprised the steps of:
(1) hydroxy-terminated silicone rubbre and silane coupling agent are mixed in mixer, prepares silicon rubber-silane coupling agent reaction
Object；The reactant and hollow glass micropearl, tetrahydrofuran are mixed, removing tetrahydrofuran is vacuumized, merging baking oven heats,
Silicon rubber-silane coupling agent-hollow glass micropearl reactant is made；
(2) silicon rubber-silane coupling agent-hollow glass micropearl reactant and filler of step (1) are mixed in mixing machine
It closes, mixture B is made；
(3) polypropylene, lubricant, peroxide, antioxidant and nucleating agent are mixed in mixing machine, mixture A is made；
(4) mixture A is added in the main spout of double screw extruder, side feed of the mixture B in double screw extruder
Material mouth is added, and after two mixtures carry out melting mixing in double screw extruder, obtains poly- the third of the wear-resisting scratch-resistant of high glaze
Alkene composite material.
In the present invention, silicon rubber-silane coupling agent reactant mixing temperature is prepared in (1) the step of the preparation method
It is 80~200 DEG C, preferably 100~120 DEG C, revolving speed is 50~150rpm, preferably 60~100rpm, incorporation time is 5~
30min, preferably 8~20min；Preparing silicon rubber-silane coupling agent-hollow glass micropearl reactant incorporation time is 1~3h,
50~200rpm of rotating speed of agitator, temperature are 25~50 DEG C, and vacuum degree is -0.07~-0.1MPa, and oven temperature is 80~100
DEG C, standing time is 1~3h.
In the present invention, the incorporation time of (2) is 5~10min the step of the preparation method, and revolving speed is 20~100rpm,
Temperature is 10~40 DEG C.
In the present invention, the incorporation time of (3) is 3~10min the step of the preparation method, and revolving speed is 20~100rpm,
Temperature is 10~40 DEG C.
In the present invention, 180-230 DEG C of extruder temperature of (4) the step of the preparation method, preferably 190-220 DEG C, revolving speed
For 200-600rpm, preferably 220-400rpm.
In the present invention, the wear-resisting scratch-resistant PP composite material of the high glaze, for processing to gloss and/or wear-resisting
The demanding high molecular material product of scraping and wiping resistance performance, preferably substitution ABS is for processing appliance shell, automotive trim strip, car door
Handle.
Mass percent " wt% " is referred both to without especially dated " % " in the present invention, vacuum degree is gauge pressure.
The positive effect of the present invention is:
1, silicon rubber-silane coupling agent-hollow glass micropearl reactant is prepared, hollow glass micropearl is made to be bound up on silicon rubber
The both ends of glue realize hollow glass micropearl and the good compatibility of silicon rubber.
2, silicon rubber and polyacrylic compatibility are poor, and silicon rubber can be with hollow glass micropearl in injection molding process
Together to the surface migration of material, to make hollow glass micropearl be mainly distributed on the surface layer of product, to realize wear-resisting scratch resistance
The effect of wiping, scratch-resistant grade Δ L≤1.0.
3, the hollow glass micropearl on surface layer is small to the influence for reducing glossiness, and the filler being affected to glossiness is in material
It is uniformly distributed in material therefore relatively fewer on surface layer, so that product be made to maintain glossiness well again, gloss value is maintained at 87
More than.
Detailed description of the invention
Fig. 1 is that the exemplar of the PP composite material processing of embodiment 1 (left side) and comparative example 1 (right side) preparation compares.
Specific embodiment
By embodiment, technical scheme is described further, but the scope of protection of present invention is not
It is confined to range described in embodiment.
Raw material information used in embodiment and comparative example is as follows:
Double screw extruder used is the Nanjing Ke Beilong Machinery Co., Ltd. product.
Scratch-resistant grade in embodiment and comparative example is tested by standard PV3952, size of sample 90*55*3mm, dermatoglyph
Number be K09, test equipment be ERICHSEN company cross scrape instrument, model 430P-I；Glossiness presses standard GB/T 9754
It tests (60o), size of sample 90*55*3mm, test equipment is the colour photometer of Hunterlab company, model UltraScan
VIS；The 3D microscope that scratch depths use Keyemce company is scraped, model VHX6000 scrapes scratch depths after test scraping；
Wear-resisting property uses plate surface brush of the plastic bruss after testing glossiness 1000 times, the friction of simulation plastics in use
Then process surveys the glossiness after friction.
Embodiment 1
Main component and dosage are as follows:
S1, polypropylene HM671T 65.889kg；
S2, silicon rubber-silane coupling agent-hollow glass micropearl reactant 10kg；
S3, talcum powder 20kg；
S4, calcium stearate 0.1kg；DTBP 0.001kg；Antioxidant 1010 2kg；NA11 2kg.
Wherein, silicon rubber-silane coupling agent-hollow glass micropearl reactant, is prepared by following component:
S2-1, hollow glass micropearl, 10 μm of average diameter, dosage 8.33kg；
S2-2, hydroxy-terminated silicone rubbre molecular weight 10,000, hydroxy-terminated silicone rubbre dosage are 1.59kg (corresponding silicon rubber-silicon
Alkane coupling agent reactant dosage is the 20% of hollow glass micropearl quality)；
S2-3, silane coupling A LINK-25, silane coupling agent dosage are 80g (corresponding hydroxy-terminated silicone rubbre quality
5%)；
Solvents tetrahydrofurane is added, tetrahydrofuran dosage is 10.02kg (silicon rubber-silane coupling agent reactant and tetrahydro
The mass ratio of furans is 1:6).
Hollow glass micropearl and coupling agent are mixed into 20min in 120 DEG C of mixers in proportion first by above-mentioned formula, turned
Speed is 100rpm, prepares silicon rubber-silane coupling agent reactant.
Above-mentioned silicon rubber-silane coupling agent reactant is mixed into 2h with hollow glass micropearl, tetrahydrofuran in proportion, is stirred
Paddle revolving speed is 150rpm, and temperature is 30 DEG C, vacuumizes removing tetrahydrofuran, and vacuum degree is -0.08MPa, and 100 DEG C of baking ovens are placed
Silicon rubber-silane coupling agent-hollow glass micropearl reactant is made in 1h.
Filler is mixed in mixing machine with above-mentioned gained silicon rubber-silane coupling agent-hollow glass micropearl reactant
5min, revolving speed 100rpm, temperature are 20 DEG C, and mixture B1 is made.
Polypropylene, nucleating agent, lubricant, peroxide and antioxidant are mixed into 5min in mixing machine, revolving speed is
80rpm, temperature are 25 DEG C, and mixture A1 is made.
By mixture A1 double screw extruder main spout be added, by mixture B1 double screw extruder side feed
Material mouth is added, and two mixtures carry out melting mixing in double screw extruder, and extrusion condition is screw speed 300rpm, screw rod
Temperature from feed inlet to head subsection setup for 180 DEG C, 185 DEG C, 185 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C,
190℃,185℃,180℃.After the PP composite material of the wear-resisting scratch-resistant of high glaze obtained is processed into exemplar, according to standard
Test performance, test result are shown in Table 1, and exemplar is shown in attached drawing 1.
Comparative example 1
By material selected by embodiment 1 (being added without coupling agent) and its corresponding proportion, referring to the technique item of embodiment 1
Part.In the comparative example, filler and hydroxy-terminated silicone rubbre, hollow glass micropearl are directly mixed to prepare mixture B in mixing machine.
It is blended by double screw extruder, after PP composite material obtained is processed into exemplar, according to identical standard test performance, is surveyed
Test result is shown in Table 1, and exemplar is shown in attached drawing 1.
Embodiment 2
Main component and dosage are as follows:
S1, polypropylene T30S 63.29kg；
S2, silicon rubber-silane coupling agent-hollow glass micropearl reactant 20kg；
S3, calcium carbonate 15kg；
S4, paraffin oil 0.01kg；DCP 0.2kg；Antioxidant 1010 0.5kg, 626 0.5kg；NA21 0.5kg；
Wherein, silicon rubber-silane coupling agent-hollow glass micropearl reactant, is prepared by following component:
S2-1, hollow glass micropearl, 50 μm of average diameter, dosage 15.38kg；
S2-2, hydroxy-terminated silicone rubbre molecular weight 15,000, hydroxy-terminated silicone rubbre dosage are that (silicon rubber-silane is even by 4.48kg
Join 30% that agent reactant dosage is hollow glass micropearl quality)；
S2-3, silane coupling A LINK-35, silane coupling agent dosage are 0.14kg (corresponding hydroxy-terminated silicone rubbre quality
3%)；
Solvents tetrahydrofurane is added, tetrahydrofuran dosage is 23.1kg (corresponding silicon rubber-silane coupling agent reactant and four
The mass ratio of hydrogen furans is 1:5)；
Hollow glass micropearl and coupling agent are mixed into 30min in 80 DEG C of mixers in proportion first by above-mentioned formula, turned
Speed is 50rpm, prepares silicon rubber-silane coupling agent reactant.
Above-mentioned silicon rubber-silane coupling agent reactant is mixed into 1h with hollow glass micropearl, tetrahydrofuran in proportion, is stirred
Paddle revolving speed is 200rpm, and temperature is 50 DEG C, vacuumizes removing tetrahydrofuran, and vacuum degree is -0.07MPa, and 90 DEG C of baking ovens place 3h,
Silicon rubber-silane coupling agent-hollow glass micropearl reactant is made.
Filler is mixed in mixing machine with above-mentioned gained silicon rubber-silane coupling agent-hollow glass micropearl reactant
8min, revolving speed 70rpm, temperature are 30 DEG C, and mixture B2 is made.
Polypropylene, nucleating agent, lubricant, peroxide and antioxidant are mixed into 3min in mixing machine, revolving speed is
100rpm, temperature are 40 DEG C, and mixture A2 is made.
By mixture A2 double screw extruder main spout be added, by mixture B2 double screw extruder side feed
Material mouth is added, and two mixtures carry out melting mixing in double screw extruder, and extrusion condition is screw speed 600rpm, screw rod
Temperature from feed inlet to head subsection setup for 195 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C,
210℃,210℃,195℃.After the PP composite material of the wear-resisting scratch-resistant of high glaze obtained is processed into exemplar, according to standard
Test performance, test result are shown in Table 1.
Comparative example 2
By material selected by embodiment 2 (being added without silicon rubber) and its corresponding proportion, referring to the technique item of embodiment 2
Part.In the comparative example, filler and coupling agent, hollow glass micropearl are directly mixed to prepare mixture B in mixing machine.By double
Screw extruder is blended, after PP composite material obtained is processed into exemplar, according to identical standard test performance, test result
It is shown in Table 1.
Embodiment 3
Main component and dosage are as follows:
S1, polypropylene BJ750 69.04kg；
S2, silicon rubber-silane coupling agent-hollow glass micropearl reactant 5kg；
S3, barium sulfate 25kg；
S4, magnesium stearate 0.5kg；Tasteless DCP 0.05kg；Antioxidant 1076 0.2kg, 168 0.2kg；
NA110.01kg；
Wherein, silicon rubber-silane coupling agent-hollow glass micropearl reactant, is prepared by following component:
S2-1, hollow glass micropearl, 100 μm of average diameter, dosage 4.348kg；
S2-2, hydroxy-terminated silicone rubbre molecular weight 120,000, hydroxy-terminated silicone rubbre dosage are 0.649kg (corresponding silicon rubber-
Silane coupling agent reactant dosage is the 15% of hollow glass micropearl quality)；
S2-3, silane coupling agent KH560, silane coupling agent dosage are 3g (the 0.5% of corresponding hydroxy-terminated silicone rubbre quality)；
Solvents tetrahydrofurane is added, tetrahydrofuran dosage is 6.52kg (silicon rubber-silane coupling agent reactant and tetrahydro furan
The mass ratio muttered is 1:10)；
Hollow glass micropearl and coupling agent are mixed into 5min in 200 DEG C of mixers in proportion first by above-mentioned formula, turned
Speed is 150rpm, prepares silicon rubber-silane coupling agent reactant.
Above-mentioned silicon rubber-silane coupling agent reactant is mixed into 3h with hollow glass micropearl, tetrahydrofuran in proportion, is stirred
Paddle revolving speed is 50rpm, and temperature is 25 DEG C, vacuumizes removing tetrahydrofuran, and vacuum degree is -0.1MPa, and 80 DEG C of baking ovens place 3h, system
Obtain silicon rubber-silane coupling agent-hollow glass micropearl reactant.
Filler is mixed in mixing machine with above-mentioned gained silicon rubber-silane coupling agent-hollow glass micropearl reactant
10min, revolving speed 20rpm, temperature are 10 DEG C, and mixture B3 is made.
Polypropylene, nucleating agent, lubricant, peroxide and antioxidant are mixed into 10min in mixing machine, revolving speed is
20rpm, temperature are 10 DEG C, and mixture A3 is made.
By mixture A3 double screw extruder main spout be added, by mixture B3 double screw extruder side feed
Material mouth is added, and two mixtures carry out melting mixing in double screw extruder, and extrusion condition is screw speed 200rpm, screw rod
Temperature from feed inlet to head subsection setup for 190 DEG C, 200 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 220 DEG C, 220 DEG C, 220 DEG C,
210℃,210℃,195℃.After the PP composite material of the wear-resisting scratch-resistant of high glaze obtained is processed into exemplar, according to standard
Test performance, test result are shown in Table 1.
Embodiment 4
Main component and dosage are as follows:
S1, polypropylene EC340Q 86.79kg；
S2, silicon rubber-silane coupling agent-hollow glass micropearl reactant 2kg；
S3, talcum powder 8kg；
S4, zinc stearate 2kg；BPO 0.01kg；Antioxidant 1010 0.1kg, 168 0.1kg；NA21 1kg；
Wherein, silicon rubber-silane coupling agent-hollow glass micropearl reactant, is prepared by following component:
S2-1, hollow glass micropearl, 2 μm of average diameter, dosage 1.818kg；
S2-2, hydroxy-terminated silicone rubbre molecular weight 20,000, hydroxy-terminated silicone rubbre dosage are 0.178kg (corresponding silicon rubber-silicon
Alkane coupling agent reactant dosage is the 10% of hollow glass micropearl quality)；
S2-3, silane coupling A LINK-35, silane coupling agent dosage are 4g (corresponding hydroxy-terminated silicone rubbre quality
2%)；
Solvents tetrahydrofurane is added, tetrahydrofuran dosage is 0.364kg (silicon rubber-silane coupling agent reactant and tetrahydro
The mass ratio of furans is 1:2)；
Hollow glass micropearl and coupling agent are mixed into 20min in 100 DEG C of mixers in proportion first by above-mentioned formula, turned
Speed is 120rpm, prepares silicon rubber-silane coupling agent reactant.
Above-mentioned silicon rubber-silane coupling agent reactant is mixed into 1.5h with hollow glass micropearl, tetrahydrofuran in proportion, is stirred
Mixing paddle revolving speed is 100rpm, and temperature is 40 DEG C, vacuumizes removing tetrahydrofuran, and vacuum degree is -0.09MPa, and 100 DEG C of baking ovens are placed
Silicon rubber-silane coupling agent-hollow glass micropearl reactant is made in 1.5h.
Filler is mixed in mixing machine with above-mentioned gained silicon rubber-silane coupling agent-hollow glass micropearl reactant
5min, revolving speed 50rpm, temperature are 40 DEG C, and mixture B4 is made.
Polypropylene, nucleating agent, lubricant, peroxide and antioxidant are mixed into 8min in mixing machine, revolving speed is
50rpm, temperature are 30 DEG C, and mixture A4 is made.
By mixture A4 double screw extruder main spout be added, by mixture B4 double screw extruder side feed
Material mouth is added, and two mixtures carry out melting mixing in double screw extruder, and extrusion condition is screw speed 400rpm, screw rod
Temperature from feed inlet to head subsection setup for 190 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C,
210℃,210℃,195℃.After the PP composite material of the wear-resisting scratch-resistant of high glaze obtained is processed into exemplar, according to standard
Test performance, test result are shown in Table 1.
Embodiment 5
Main component and dosage are as follows:
S1, polypropylene EP548RQ 84.07kg；
S2, silicon rubber-silane coupling agent-hollow glass micropearl reactant 8kg；
S3, barium sulfate 5kg；
S4, white oil 0.8kg；DCP 0.03kg；Antioxidant 1076 0.2kg, 168 0.4kg；NA11 1.5kg；
Wherein, silicon rubber-silane coupling agent-hollow glass micropearl reactant, is prepared by following component:
S2-1, hollow glass micropearl, 1 μm of average diameter, dosage 7.619kg；
S2-2, hydroxy-terminated silicone rubbre molecular weight 30,000, hydroxy-terminated silicone rubbre dosage are 0.372kg (corresponding silicon rubber-silicon
Alkane coupling agent reactant dosage is the 5% of hollow glass micropearl quality)；
S2-3, silane coupling A LINK-25, silane coupling agent dosage are 9g (corresponding hydroxy-terminated silicone rubbre quality
2.5%)；
Solvents tetrahydrofurane is added, tetrahydrofuran dosage is 3.048kg (silicon rubber-silane coupling agent reactant and tetrahydro
The mass ratio of furans is 1:8)；
Hollow glass micropearl and coupling agent are mixed into 15min in 110 DEG C of mixers in proportion first by above-mentioned formula, turned
Speed is 80rpm, prepares silicon rubber-silane coupling agent reactant.
Above-mentioned silicon rubber-silane coupling agent reactant is mixed into 2h with hollow glass micropearl, tetrahydrofuran in proportion, is stirred
Paddle revolving speed is 120rpm, and temperature is 30 DEG C, vacuumizes removing tetrahydrofuran, and vacuum degree is -0.08MPa, and 100 DEG C of baking ovens are placed
Silicon rubber-silane coupling agent-hollow glass micropearl reactant is made in 2h.
Filler is mixed in mixing machine with above-mentioned gained silicon rubber-silane coupling agent-hollow glass micropearl reactant
5min, revolving speed 90rpm, temperature are 25 DEG C, and mixture B5 is made.
Polypropylene, nucleating agent, lubricant, peroxide and antioxidant are mixed into 4min in mixing machine, revolving speed is
60rpm, temperature are 20 DEG C, and mixture A5 is made.
By mixture A5 double screw extruder main spout be added, by mixture B5 double screw extruder side feed
Material mouth is added, and two mixtures carry out melting mixing in double screw extruder, and extrusion condition is screw speed 500rpm, screw rod
Temperature from feed inlet to head subsection setup for 190 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 220 DEG C, 220 DEG C,
210℃,210℃,195℃.After the PP composite material of the wear-resisting scratch-resistant of high glaze obtained is processed into exemplar, according to standard
Test performance, test result are shown in Table 1.
The performance of table 1 embodiment and comparative example exemplar
| Glossiness | Glossiness after friction | Scratch-resistant grade Δ L | Scrap marks depth μm | |
| Embodiment 1 | 89 | 80 | 0.8 | 220 |
| Comparative example 1 | 37 | 11 | 4.7 | 421 |
| Embodiment 2 | 88 | 83 | 1.0 | 218 |
| Comparative example 2 | 53 | 24 | 6.3 | 386 |
| Embodiment 3 | 87 | 84 | 0.9 | 180 |
| Embodiment 4 | 91 | 89 | 0.8 | 235 |
| Embodiment 5 | 89 | 85 | 0.5 | 137 |
The exemplar that the performance test results of table 1 show that the PP composite material of embodiment preparation is processed into has bloom
The characteristics of damp, wear-resisting scratch-resistant.
Claims (12)
1. a kind of wear-resisting scratch-resistant PP composite material of high glaze, is prepared by following component:
S1, polypropylene, 60%~90%, preferably 65%~85%；
S2, silicon rubber-silane coupling agent-hollow glass micropearl reactant, 2%~20%, preferably 5%~10%；
S3, filler, 5~30%, preferably 10~20%；
S4, auxiliary agent packet, contain lubricant 0.01%~2%, preferably 0.2%~1%, peroxide 0.001%~0.2%, preferably
0.01%~0.1%, antioxidant 0.1%~2%, preferably 0.2%~1%, nucleating agent 0.01%~2%, preferably 0.2%~
1%；
The ratio of the above component is based on PP composite material gross mass.
2. PP composite material according to claim 1, which is characterized in that the polypropylene that S1 is selected is homopolypropylene
And/or copolymer polypropylene, melting means range are 1-60g/10min, preferably melting means range is 3-30g/10min.
3. PP composite material according to claim 1, which is characterized in that S2 is prepared by following component:
S2-1, hollow glass micropearl；
S2-2, hydroxy-terminated silicone rubbre react to obtain silicon rubber-silane coupling agent reactant with silane coupling agent, and reactant is used
Amount is the 5%~30% of hollow glass micropearl quality, preferably 10%~20%；
S2-3, silane coupling agent, silane coupling agent dosage be hydroxy-terminated silicone rubbre quality 0.5%~5%, preferably 1%~
3%；
Organic solvent need to be added when preparing S2, organic solvent is preferably tetrahydrofuran, organic solvent and silicon rubber-silane coupling agent
The mass ratio of reactant is (2~10): 1, preferably (4~6): 1.
4. PP composite material according to claim 3, which is characterized in that the hollow glass micropearl diameter that S2-1 is selected
It is 1~100 μm, preferably 2~50 μm；The hydroxy-terminated silicone rubbre molecular weight that S2-2 is selected is 10,000~150,000, preferably 15,
000~50,000；The silane coupling agent that S2-3 is selected is γ-glycidyl ether oxygen propyl trimethoxy silicane, 3- isocyanic acid third
One of ethyl triethoxy silicane alkane and 3- isocyanatopropyl trimethoxy silane are a variety of, preferably three ethoxy of 3- isocyanatopropyl
Base silane and/or 3- isocyanatopropyl trimethoxy silane.
5. PP composite material according to claim 1, which is characterized in that the filler that S3 is selected is barium sulfate, carbonic acid
One of calcium and talcum powder are a variety of.
6. PP composite material according to claim 1, which is characterized in that the lubricant in S4 auxiliary agent packet is stearic acid
One of calcium, zinc stearate, magnesium stearate, white oil and paraffin oil are a variety of；Peroxide is cumyl peroxide, peroxide
Change benzoyl, two-(t-butylperoxyisopropyl) one of benzene and di-tert-butyl peroxide or a variety of；Antioxidant is
1010, one of 1076,168 and 626 or a variety of；Nucleating agent is NA11 and/or NA21.
7. the preparation method of PP composite material of any of claims 1-6, which is characterized in that include following system
Standby step:
(1) hydroxy-terminated silicone rubbre and silane coupling agent are mixed in mixer, prepares silicon rubber-silane coupling agent reactant；
The reactant and hollow glass micropearl, tetrahydrofuran are mixed, removing tetrahydrofuran, merging baking oven heating, system are vacuumized
Obtain silicon rubber-silane coupling agent-hollow glass micropearl reactant；
(2) silicon rubber-silane coupling agent-hollow glass micropearl reactant and filler of step (1) are mixed in mixing machine, is made
Obtain mixture B；
(3) polypropylene, lubricant, peroxide, antioxidant and nucleating agent are mixed in mixing machine, mixture A is made；
(4) mixture A is added in the main spout of double screw extruder, side spout of the mixture B in double screw extruder
It is added, after two mixtures carry out melting mixing in double screw extruder, the polypropylene for obtaining the wear-resisting scratch-resistant of high glaze is multiple
Condensation material.
8. preparation method according to claim 7, which is characterized in that it is anti-to prepare silicon rubber-silane coupling agent in step (1)
The mixing temperature for answering object is 80~200 DEG C, and preferably 100~120 DEG C, revolving speed is 50~150rpm, preferably 60~100rpm, mixing
Time is 5~30min, preferably 8~20min；When preparing the mixing of silicon rubber-silane coupling agent-hollow glass micropearl reactant
Between be 1~3h, 50~200rpm of rotating speed of agitator, temperature be 25~50 DEG C, vacuum degree be -0.07~-0.1MPa, oven temperature
It is 80~100 DEG C, standing time is 1~3h.
9. preparation method according to claim 7, which is characterized in that the incorporation time of step (2) is 5~10min, revolving speed
For 20~100rpm, temperature is 10~40 DEG C.
10. preparation method according to claim 7, which is characterized in that the incorporation time of step (3) is 3~10min, is turned
Speed is 20~100rpm, and temperature is 10~40 DEG C.
11. preparation method according to claim 7, which is characterized in that 180-230 DEG C of extruder temperature of step (4), preferably
190-220 DEG C, revolving speed 200-600rpm, preferably 220-400rpm.
12. system described in any one of PP composite material of any of claims 1-6 or claim 7-11
The wear-resisting scratch-resistant PP composite material of high glaze made from Preparation Method, for processing to gloss and/or wear-resisting scraping and wiping resistance performance
Demanding high molecular material product, preferably substitution ABS is for processing appliance shell, automotive trim strip, door handle.
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