CN101870784B - Impact resisting weather-proof polypropylene and preparation method thereof - Google Patents
Impact resisting weather-proof polypropylene and preparation method thereof Download PDFInfo
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- CN101870784B CN101870784B CN2010101387545A CN201010138754A CN101870784B CN 101870784 B CN101870784 B CN 101870784B CN 2010101387545 A CN2010101387545 A CN 2010101387545A CN 201010138754 A CN201010138754 A CN 201010138754A CN 101870784 B CN101870784 B CN 101870784B
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Abstract
The invention discloses impact resisting weather-proof polypropylene and a preparation method thereof. The impact resisting weather-proof polypropylene comprises the following components in percentage by weight: 55-78 percent of polypropylene, 5-15 percent of polyethylene, 15-30 percent of filler, 0.2-1.0 percent of antioxygen, 0.2-1.0 percent of light stabilizer and 0.2-1.0 percent of coupling agent. The obtained polypropylene material has excellent liquidity as well as excellent impact performance and weather resistance.
Description
Technical field
The present invention relates to the polypropylene modification technical field, specifically, relate to a kind of impact resisting weather-proof polypropylene material and preparation method thereof.
Background technology
Vestolen PP 7052 (PP) is inexpensive because of its high comprehensive performance, wide material sources, light weight, therefore is widely used in every field.But the PP part that also comes with some shortcomings, disadvantage are that winter hardiness is poor, fragile under low temperature disconnected; Next is that PP shock resistance after filling-modified is poor, and shortcoming such as be prone to break after product falls; Moreover because PP contains unsettled tertiary carbon group, degradation with aging be prone to take place after light, heat, oxygen effect and cause problems such as degradation and variable color.These shortcomings have all limited the use of PP, have especially limited the PP application on the goods out of doors, particularly for the product that is placed with for a long time shock resistance and weather-proof requirement out of doors, must improve the shock resistance of PP and the Application Areas that weathering resistance could be expanded PP.
Present traditional anti-impact weather-proof polypropylene generally adopts inorganic filler to fill, and improves impact property through adding toughner, adds photostabilizer simultaneously and improves weathering resistance.Toughner is generally selected rubber or other elastomerics, like ethylene-propylene rubber(EPR) (EPR), ethylene-propylene-diene terpolymers (EPDM), styrene-butadiene-styrene multipolymer (SBS), ethylene-octene copolymer elastomericss such as (POE).But rubber or elastomerics price are relatively expensive; Rubber or elastomeric use simultaneously also can weaken rigidity, thermotolerance and the flowability of material; Part rubber such as EPDM, SBS are because of containing the part unsaturated double-bond; So its heatproof oxidation performance ability, weathering resistance also can descend to some extent, cause the outward appearance and the degradation of the finished product.Secondly; Employed photostabilizer is generally the steady surely agent of single component hindered amine light; Perhaps composite an amount of UV light absorber, but often do not consider consistency and photostabilizer stability in environment for use of antagonistic effect, photostabilizer and resin between synergistic effect, photostabilizer and the part oxidation inhibitor between the photostabilizer etc.If select improperly, photostabilizer not only can not play the stable effect of light, but also can accelerated material aging, do not reach expected effect.Moreover; Weighting agent generally all is mixed together the back from the same charging opening blanking of forcing machine with other material; This can cause oxidation inhibitor and photostabilizer to be filled the agent absorption easily; Thereby oxidation inhibitor and photostabilizer can not be brought into play maximum effect, cause the thermal-oxidative aging property of material and weather resistance to descend significantly.In Chinese invention patent 200610053335.5; Disclose a kind of modified, weather resisting polypropylene material, but the plasticized modifier consumption is too much, causes comprehensive mechanical performance bad; And the weather resistance of material neither be fine, is difficult to guarantee secular weather-proof requirement.
Summary of the invention
The object of the invention is exactly in order to overcome existing impact resisting weather-proof polypropylene cost costliness, flowability and the bad shortcoming of weathering resistance, a kind of have excellent flowability, the impact property of excellence and the impact resisting weather-proof polypropylene of weather resistance to be provided.
Another object of the present invention provides the preparation method of above-mentioned impact resisting weather-proof polypropylene.
In order to realize above purpose, impact resisting weather-proof polypropylene of the present invention is made up of following weight percent:
A kind of impact resisting weather-proof polypropylene comprises following component and weight percent:
Vestolen PP 7052 55%-78%
Vilaterm 5%-15%
Weighting agent 15%-30%
Oxidation inhibitor 0.2%-1.0%
Photostabilizer 0.2%-1.0%
Coupling agent 0.2%-1.0%.
In above-mentioned impact resisting weather-proof polypropylene, also comprise processing aid 0.2 ~ 0.8 weight %, tinting material 0.5 ~ 1.0 weight %.
In above-mentioned impact resisting weather-proof polypropylene, said Vestolen PP 7052 is a kind of or its mixture in HOPP, COPP, the atactic copolymerized polypropene, melt flow rate(MFR) be 1.5g/10min-35g/10min (230 ℃/2.16kg).
In above-mentioned impact resisting weather-proof polypropylene; Said Vilaterm is a kind of or its mixture in high density polyethylene(HDPE) (HDPE), linear low density polyethylene (LLDPE), the new LDPE (film grade) (LDPE), melt flow rate(MFR) be 1.0g/10min-10g/10min (190 ℃/2.16kg).
In above-mentioned impact resisting weather-proof polypropylene; Said weighting agent is a kind of or its mixture in talcum powder, lime carbonate, permanent white, calcium sulfate, wollastonite, mica, the silicon-dioxide, and its effect is to make material favorable rigidity and thermotolerance and increase dimensional stability arranged, can also reduce cost simultaneously.
In above-mentioned impact resisting weather-proof polypropylene, said oxidation inhibitor is the mixture of primary antioxidant, auxiliary anti-oxidant and metallic ion passivation agent class, and its effect is the thermo-oxidative stability that improves in processing and the use, avoids colour properties to change.Wherein primary antioxidant is a Hinered phenols, can select IRGANOX 1010, IRGANOX 1076, IRGANOX 3114, CYANOX1790, ANOX330 etc.; Auxiliary anti-oxidant is the phosphorous acid esters that molecular weight is big, chemicalstability is good, can select IRGAFOS 168, IRGAFOS 126, IRGAFOS P-EPQ, Ultranox 627A etc.; The metallic ion passivation agent is that a kind of material and metallic contact of preventing causes the auxiliary anti-oxidant class of thermooxidative degradation, can select IRGANOX MD1024.
In above-mentioned impact resisting weather-proof polypropylene, said photostabilizer is the mixture of hindered amine light stabilizer, UV light absorber, and its effect is thermo-oxidative stability and the weathering resistance that improves in the product use, avoids colour properties to change.Wherein hindered amine light stabilizer is a kind of mixture, comprises the high-molecular weight hindered amine light stabilizer, can select CHIMASSORB944, CHIMASSORB 2020, TINUVIN 622 etc.; Also comprise low molecular weight hindered amine class photostabilizer, can select TINUVIN 770, Uvinul 4050H, Cyasorb UV 3853 etc.; And the NOR type hindered amine as light stabilizer of low alkalinity, can select TINUVIN 123S, TINUVIN NOR 371, TINUVIN XT855 etc.UV light absorber is the hydroxybenzotriazole class, can select TINUVIN 234, TINUVIN 326, TINUVIN 327 etc.Said coupling agent is a kind of or its mixture in titanate coupling agent, the silane coupling agent.The optional monoalkoxytitanates coupling agent of titanate coupling agent (NDZ-101), sec.-propyl three oleic acid acyloxy titanic acid ester (NDZ-105); The optional γ-An Bingjisanyiyangjiguiwan of silane coupling agent (KH-550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570).
In above-mentioned impact resisting weather-proof polypropylene, said processing aid is a kind of or its mixture of low molecule ester class, metallic soap class, Triple Pressed Stearic Acid complex ester class, amides.Specifically comprise low molecular polyethylene, calcium stearate (CAST), Zinic stearas (ZNST), erucicamide and N; N-ethylene bis stearic acid amide (EBS), low-viscosity bisphenol A epoxide resin (Araldite GT7071) etc.; It mainly acts on is in processing and moulding process, to improve the dispersed of each component and prevent that weighting agent from absorbing oxidation inhibitor and photostabilizer, plays the effect of protection oxidation inhibitor and photostabilizer.
The preparation method of above-mentioned impact resisting weather-proof polypropylene comprises the steps:
The 1st step: take by weighing each starting material by weight;
The 2nd step: acrylic resin, polyvinyl resin, oxidation inhibitor, part coupling agent, photostabilizer, processing aid and tinting material were mixed in mixing machine 3-8 minute, obtain mixture; The 3rd step: mixed about 3-8 minute in high-speed mixer (rotating speed is not less than 800RPM) by the coupling agent and the weighting agent of proportioning, obtain mixture with remainder;
The 4th step: the mixture of the mixture of step 2 and step 3 respectively from the main charging opening and the side loading mouth blanking extruding pelletization of twin screw extruder, is finally obtained product.Processing temperature is 190-230 ℃, and screw speed is 300-450RPM, and screw slenderness ratio is not less than 32, and the extruder temperature controller district is not less than 9 districts, and the side loading mouth is positioned at the 4th or the 5th district.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention has carried out careful screening to oxidation inhibitor and photostabilizer.The high molecular weight hindered phenols kind antioxidant that oxidation inhibitor is preferably good with resin compatible, chemicalstability is good, composite phosphorous acid esters auxiliary anti-oxidant and metallic ion passivation agent simultaneously; And the mixture of the NOR type hindered amine as light stabilizer of the preferred HMW of photostabilizer and low-molecular-weight hindered amine as light stabilizer and low alkalinity, composite UV light absorber simultaneously.Wherein, the high-molecular weight hindered amine as light stabilizer is as a kind of long-acting photostabilizer, its Heat stability is good, reaches the chemicalstability excellence well with the consistency of resin; And low-molecular-weight photostabilizer is especially splendid to thin wall parts protection effect owing to can slowly moving the protecting materials outward appearance effect of playing to material surface; And the NOR type hindered amine as light stabilizer of low alkalinity is owing to react to each other with acidic components, and therefore the synergistic effect with the auxiliary anti-oxidant of phosphorous acid esters is fabulous, and the while also is specially adapted in the sour environment, like the intensive area of acid rain; And UV light absorber optionally absorbs ultraviolet ray, makes it to become harmless energy and discharges or consume, and also plays the effect of coordinating protection material.Resulting material has the impact property and the weather resistance of excellent flowability, excellence.
2. in preparation method of the present invention, in order to make oxidation inhibitor and photostabilizer performance maximum effect, special that weighting agent is reinforced from the side loading mouth.Because through this kind feed way; Weighting agent with other material before twin screw is joined; Oxidation inhibitor and photostabilizer fully fuse into resin; And processing aid (like EBS, Araldite GT7071) can form resist at resin surface layer, except lubrication, can also prevent weighting agent absorption oxidation inhibitor and photostabilizer and weaken the effect of oxidation inhibitor and photostabilizer; The present invention simultaneously for the effect of bringing into play coupling agent better, improve consistency between weighting agent and the resin, special weighting agent is used separately after the part coupling agent activation treatment from the blanking of side loading mouth.
Embodiment
The preparation method of embodiment is:
The 1st step: take by weighing each starting material by weight;
The 2nd step: acrylic resin, polyvinyl resin, oxidation inhibitor, part coupling agent, photostabilizer, processing aid and tinting material were mixed in mixing machine 5 minutes, obtain mixture;
The 3rd step: mixed about 6 minutes in high-speed mixer (rotating speed 1200RPM) by the coupling agent and the weighting agent of proportioning, obtain mixture with remainder;
The 4th step: the mixture of the mixture of step 2 and step 3 respectively from the main charging opening and the side loading mouth blanking extruding pelletization of twin screw extruder, is finally obtained product.Processing temperature is 200 ℃, and screw speed is 450RPM, screw slenderness ratio 32, and 11 districts, extruder temperature controller district, the side loading mouth is positioned at the 4th district.
The concrete composition of comparative example and embodiment is listed in table 1, and traditional performance is listed in table 2.
Table 1
Table 2
Table 3, table 4 were respectively the prepared impact resisting weather-proof polypropylene xenon lamp aging of comparative example 2, embodiment 2 2500 hours, and the mechanical property conservation rate in 10000 hours (area, Guangzhou) is exposed to the sun in the open air; Table 5 is employed standard for the present invention tests.
Table 3
Table 4
Table 5
Claims (8)
1. impact resisting weather-proof polypropylene is characterized in that comprising following component and weight percent:
Described oxidation inhibitor is the mixture of Hinered phenols primary antioxidant, phosphorous acid esters auxiliary anti-oxidant and metallic ion passivation agent;
Described photostabilizer is the mixture of hindered amine light stabilizer and UV light absorber; Said hindered amine light stabilizer is the mixture of the NOR type hindered amine as light stabilizer of HMW and low-molecular-weight hindered amine as light stabilizer and low alkalinity.
2. impact resisting weather-proof polypropylene according to claim 1 is characterized in that: also comprise processing aid 0.2～0.8 weight %, tinting material 0.5～1.0 weight %.
3. impact resisting weather-proof polypropylene according to claim 1 is characterized in that: described acrylic resin is a kind of or its mixture in HOPP, the COPP.
4. impact resisting weather-proof polypropylene according to claim 1 is characterized in that: described Vilaterm is one or more the mixture in high density polyethylene(HDPE), linear low density polyethylene, the new LDPE (film grade).
5. impact resisting weather-proof polypropylene according to claim 1 is characterized in that: described weighting agent is one or more the mixture in talcum powder, lime carbonate, permanent white, calcium sulfate, wollastonite, mica, the silicon-dioxide.
6. impact resisting weather-proof polypropylene according to claim 1 is characterized in that: described coupling agent is a kind of or its mixture in titanate coupling agent, the silane coupling agent.
7. impact resisting weather-proof polypropylene according to claim 2 is characterized in that: described processing aid is one or more mixture of low molecule ester class, metallic soap class, Triple Pressed Stearic Acid complex ester class, amides and low-viscosity bisphenol A epoxide resin.
8. the preparation method of the described impact resisting weather-proof polypropylene of claim 2 is characterized in that comprising the steps:
(1) takes by weighing each starting material by weight;
(2) acrylic resin, polyvinyl resin, oxidation inhibitor, part coupling agent, photostabilizer, processing aid and tinting material were mixed in mixing machine 3-8 minute, obtain mixture;
(3) in high-speed mixer, mixed 3-8 minute by the coupling agent and the weighting agent of proportioning with remainder, rotating speed is not less than 800RPM, obtains mixture;
(4) with the mixture of the mixture of step 2 and step 3 respectively from the main charging opening and the side loading mouth blanking extruding pelletization of twin screw extruder; Finally obtain product; Processing temperature is 190-230 ℃, and screw speed is 300-450RPM, and screw slenderness ratio is not less than 32; The extruder temperature controller district is not less than 9 districts, and the side loading mouth is positioned at the 4th or the 5th district.
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