CN102952341B - High-rigidity-toughness low-odor polypropylene composition and preparation method thereof - Google Patents
High-rigidity-toughness low-odor polypropylene composition and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polypropylene materials, and particularly relates to a high-rigidity-toughness low-odor polypropylene composition and a preparation method thereof. The high-rigidity-toughness low-odor polypropylene composition is prepared from the following raw materials in parts by mass: 60-90 parts of low-odor impact polypropylene, 5-35 parts of talcum powder, 3-10 parts of toughener, 0.5-5 parts of white carbon black and 0.2-0.8 part of composite antioxidant. The preparation method of the composition comprises the following steps: uniformly performing dry-mixing on the raw materials in a high-speed mixer according to the ratio, wherein the rotation speed of the mixer is 400-500 rpm, and the dry-mixing time is 5-10 minutes; and extruding and granulating with an extruding machine at 170-220 DEG C. The composition provided by the invention can achieve a low odor level, has high impact strength and rigidity and is low in cost; and the preparation process is simple and easy to implement. The composition can be used for the production of automobile parts and home appliance parts.
Description
Technical field
The invention belongs to polypropylene material technical field, be specifically related to a kind of high strong and unyielding low odor polypropylene composition and method of making the same.
Background technology
The advantages such as density is little owing to having, good heat resistance, intensity are high for polypropylene, have excellent resistance to water soak, antiacid caustic corrosion, resist dissolution, have developed into the second largest general-purpose plastics except polyethylene at present.Modified polypropene improves further by adding various properties-correcting agent and expands Properties of Polypropylene exactly, makes it obtain and applies widely, can be used for each large fields such as automobile, household electrical appliances, daily necessities.But polypropylene itself and various additive can make the matrix material of preparation with larger odor profiles usually, make its feature of environmental protection not reach service requirements.Along with the fast development of each industrial circle and the raising day by day of people's living standard, more, higher requirement is proposed to polypropylene modified material, except will improving mechanical property, fluidity of molten, also more and more higher to the odor profiles requirement of material.And polyacrylic rigidity and toughness are restrictions mutually, rigidity raising can cause toughness decline to a certain degree, and vice versa, and therefore how obtaining rigid-tough balance is the focus that people study.
With regard to how obtaining high-performance there is again the modified polypropylene material of low smell simultaneously, also having the research of some patents and document to report.
The people such as Weng Yonghua propose a kind of low smell, low-volatile polypropylene composite material in patent CN 1727389A, it is the performance by adopting the way of Kiselgel A to realize its low smell, low-volatile, the polypropylene used is the one in high crystalline homopolypropylene or block copolymerization polypropylene or its combination, wherein the comonomer of block copolymerization polypropylene is common is ethene, and its content is in the scope of 4-10mol%.
The people such as Gu Chun propose a kind of low modified polypropylene composite material distributed and preparation method thereof in patent CN 101817953A, are to be shared by kind of the mixture of three in clay, wilkinite, porous silica, activated alumina or molecular sieve that to reduce matrix material as odor adsorption agent odor profiles.
Kim, the people such as Hee-Soo (being published in Journal of Applied Polymer Science (2008), 110 (5): 3247-3255) have studied the impact that zeolite type and content discharge natural powder filling polypropylene composite material mechanical property, thermal characteristics, smell and volatile organic matter VOC.Result shows, zeolite effectively can reduce smell and the VOC quantity discharged that nature powder fills thermoplastic polymer composite material, does not affect mechanical property and the thermal characteristics of material simultaneously.
The people such as Zhou Yinghui propose a kind of high-performance low-odour polypropylene dedicated for automobile dashboard and preparation method thereof in patent CN 1840576A, the smell properties-correcting agent of its practicality is inorganic powder molecular sieve, when the modulus in flexure of material at 23 DEG C reaches 2400MPa, Izod notched impact strength still can reach 42kJ/m
2above; Smell rank can reach more than 6 grades of GM standard.
The system mechanical property defectiveness that above-mentioned research has, although resistance to impact shock as high in rigidity is low; The raw material of some employings itself is greatly odor profiles, carries it into composite system, and the system smell of making cannot reach lower level.
Summary of the invention
The object of this invention is to provide a kind of high strong and unyielding low odor polypropylene composition and method of making the same, by adopting the polypropylene base resin of a kind of low smell, high impact-resistant, the composite antioxidant of two kinds of high-melting-points, low-volatile, and a kind of odor suppressing agents that effectively can reduce composition material smell, prepare a kind of low smell of low cost, the polypropene composition of high impact properties.
The strong and unyielding low-odor polypropylene ene compositions of height of the present invention, be made up of the raw material of following parts by weight:
Described low smell impact polypropylene is low smell High Impact Polypropylene resin, and its preparation method is as follows: by 100 parts, Co-polypropylene powder; Composite antioxidant 31,14/,330 0.4 parts; Acid-acceptor Cast 0.1 part; Lubricants GMS 0.1 part, fully after mixing, makes through twin screw extruder extruding pelletization.Forcing machine each district temperature is 170 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 210 DEG C, and screw speed is 200 ~ 300rpm, and granulation screw adopts and vacuumizes, vacuum tightness 0.3MPa.Co-polypropylene powder degree of isotacticity more than 95%, in every kg polypropylene, catalyst residue is less than 0.02g, its comonomer ethylene content 6 ~ 13mol%, preferably 11 ~ 13mol%; The composite mass ratio of both composite antioxidants 3114/330,3114 and 330 is 1.0.The low smell High Impact Polypropylene resin melt mass flow rate prepared is 7 ~ 30g/10min, why preferably 8 ~ 11g/10min, select low smell High Impact Polypropylene to be rigidity for composition provides and shock resistance and to reduce as far as possible to bring smell into.
Described amount of talc is 18 ~ 25 parts, and particle diameter is 1000 ~ 5000 orders, preferably 1000 ~ 2000 orders.
Described toughner is ethylene-octene copolymer (being called for short POE), and consumption is 7 ~ 10 parts, and density is 0.88 ~ 0.90g/cm
3.
Described white carbon black is 3 ~ 5 parts, and median size is 1000 ~ 5000 orders, preferred 3000-5000 order, and BET method specific surface area is 50 ~ 500m
2/ g.As the odor suppressing agents in composition, smell that is that each component of active adsorption has and that produce in processing, use, and also white carbon black self color and luster is close with polypropylene, composition color can be made to keep better, and be conducive to being deployed into other color.
Described composite antioxidant consumption preferably 0.7 ~ 0.8 part, composite antioxidant is high-melting-point, the primary antioxidant of low-volatile and the mixture of auxiliary anti-oxidant, and the fusing point of primary antioxidant and auxiliary anti-oxidant requires as 218-224 DEG C, fugitive constituent≤0.1%.The preferred primary antioxidant 3114 of the present invention, chemical name is 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, the preferred auxiliary anti-oxidant 330 of the present invention, chemical name is 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene.Both compound proportions is 1: 1 ~ 2, preferably 1: 1 ~ 1.5.
The preparation method of height of the present invention strong and unyielding low-odor polypropylene ene compositions is as follows: be first dry mixed in super mixer by the material of formula ratio evenly, mixing machine rotating speed is 400 ~ 500 revs/min, the time of being dry mixed is 5 ~ 10min, then makes through forcing machine extruding pelletization at 170 ~ 220 DEG C.
Beneficial effect of the present invention is as follows:
(1) the present invention uses low smell high impact resistance polypropylene resin to be basic raw material, use the high efficiency composition oxidation inhibitor of high-melting-point, low-volatile, low smell, adopt efficient odor suppressing agents again, obtained composition can reach lower oder levels simultaneously;
(2) the present invention adopts the acrylic resin of high-impact to be raw material, even if the mineral filler of interpolation high level is as talcum powder etc., can still keep higher resistance to impact shock;
(3) cost of the present invention is low, and preparation is simple;
(4) composition that prepared by the present invention can be used for requiring the higher field such as automobile, household electrical appliances to mechanical property and the feature of environmental protection, promotes this art progress, has huge economic benefit and social benefit.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Product of the present invention adopts national standard and germany volkswagen company standard to detect.Concrete testing method is as follows:
1, melt mass flow rate (MFR) is undertaken by GB/T 3682-2000, load 2.16kg;
2, stretching yield stress, fracture norminal strain are undertaken by GB/T 1040-2006, I type batten, and draw speed is 50mm/min;
3, Izod notched impact strength is undertaken by GB/T 1843-2008, and wherein low-temperature process is-20 DEG C of placements 2 hours, and normal temperature treating processes is 23 DEG C and places 24 hours;
4, bending elastic modulus, flexural strength are undertaken by GB/T 9341-2008;
5, odor profiles test is carried out according to the method for germany volkswagen standard P V3900, and the judgment criteria of its oder levels is: not easily feel for grade 1, can feel but not be pungent for grade 2, obviously can feel but not be pungent for grade 3, be pungent for class 4, be very pungent for class 5, can not stand as class 6.
Embodiment 1 ~ 6
The preparation method of low smell impact polypropylene is as follows: by 100 parts, Co-polypropylene powder; Composite antioxidant 3114/3300.4 part; Acid-acceptor Cast 0.1 part; Lubricants GMS 0.1 part, fully after mixing, makes through twin screw extruder extruding pelletization.Forcing machine each district temperature is 170 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 210 DEG C, and screw speed is 250 ± 50rpm, and granulation screw adopts and vacuumizes, vacuum tightness 0.3 MPa.Co-polypropylene powder degree of isotacticity 95%, in every kg polypropylene, catalyst residue is less than 0.02g, and the composite mass ratio of both composite antioxidants 3114/330,3114 and 330 is 1.0.
The component of the strong and unyielding low-odor polypropylene of the height described in embodiment 1 ~ 6 ene compositions, proportioning and performance index are as shown in table 1.
Height described in embodiment 1 ~ 6 strong and unyielding low odor polypropylene preparation method of composition is as follows: take each raw material by formula ratio, 7 ± 1 minutes are uniformly mixed in high-speed mixer, mixing machine rotating speed is 450 ± 50 revs/min, after discharging in twin screw extruder extruding pelletization, forcing machine each district temperature is 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 220 DEG C, 210 DEG C, and screw speed is 200 ~ 300rpm.
Table 1 embodiment 1 ~ 6 component, proportioning and performance index table
Comparative example 1 ~ 2
The component of the polypropene composition described in comparative example 1 ~ 2, proportioning and performance index are as shown in table 2.
The preparation method of comparative example 1 ~ 2 is as embodiment 1 ~ 6.
Table 2 comparative example component, proportioning and performance index table
| Composition and performance | Comparative example 1 | Comparative example 2 |
| Plain polypropylene | 70.8 | 67.8 |
| Talcum powder | 20 | 20 |
| POE | 9 | 9 |
| Common commercially available oxidation inhibitor 1 | 0.1 | 0.1 |
| Common commercially available oxidation inhibitor 2 | 0.1 | 0.1 |
| White carbon black | 0 | 4 |
| Melt mass flow rate, g/10min | 8.7 | 8.8 |
| Stretching yield stress, MPa | 18.7 | 19.2 |
| Fracture norminal strain, % | 65 | 83 |
| Stress in bending | 30.6 | 29.8 |
| Bending elastic modulus, MPa | 1950 | 1877 |
| Izod notched impact strength 23 DEG C, kJ/m 2 | 12.3 | 13.9 |
| Izod notched impact strength-20 DEG C, kJ/m 2 | 3.4 | 3.7 |
| Load deformation temperature, DEG C | 113 | 110 |
| Oder levels | 4.0 | 3.5 |
From embodiment and comparative example performance test results, when adopting plain polypropylene, common oxidation inhibitor, when identical POE consumption, the toughness of comparative example is lower, smell is comparatively large, and rigid phase is worked as; When adopting plain polypropylene, common oxidation inhibitor, when adopting the white carbon black of same amount, the oder levels of comparative example decreases, but still higher than embodiment.
Claims (8)
1. a high strong and unyielding low-odor polypropylene ene compositions, is characterized in that being made up of the raw material of following parts by weight:
Impact polypropylene 60 ~ 90
Talcum powder 5 ~ 35
Toughner 3 ~ 10
White carbon black 0.5 ~ 5
Composite antioxidant 0.2 ~ 0.8;
Described impact polypropylene is low smell High Impact Polypropylene resin, and its comonomer ethylene content is 6 ~ 13mol%, and its melt mass flow rate is 7 ~ 30g/10min;
Described composite antioxidant is the mixture of primary antioxidant 3114 and auxiliary anti-oxidant 330, and its composite mass ratio is 1:1 ~ 2;
The preparation method of described low smell High Impact Polypropylene resin is as follows: by 100 parts, Co-polypropylene powder; Composite antioxidant 31,14/,330 0.4 parts; Acid-acceptor Cast 0.1 part; Lubricants GMS 0.1 part, fully after mixing, makes through twin screw extruder extruding pelletization; Forcing machine each district temperature is 170 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 210 DEG C, and screw speed is 200 ~ 300rpm, and granulation screw adopts and vacuumizes, vacuum tightness 0.3 MPa; Co-polypropylene powder degree of isotacticity more than 95%, in every kg polypropylene, catalyst residue is less than 0.02g; Composite mass ratio in composite antioxidant 3114/330 both 3114 and 330 is 1.0.
2. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1, it is characterized in that described low smell High Impact Polypropylene resin, its comonomer ethylene content is 11 ~ 13mol%, and its melt mass flow rate is 8 ~ 11g/10min.
3. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1, it is characterized in that described amount of talc is 18 ~ 25 parts, particle diameter is 1000 ~ 5000 orders.
4. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 3, is characterized in that described talcous particle diameter is 1000 ~ 2000 orders.
5. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1, it is characterized in that described toughner is POE, consumption is 7 ~ 10 parts.
6. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1, it is characterized in that described white carbon black is 3 ~ 5 parts, median size is 1000 ~ 5000 orders, and BET method specific surface area is 50 ~ 500m
2/ g.
7. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 6, is characterized in that described white carbon black median size is 3000 ~ 5000 orders.
8. the preparation method of the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1, it is characterized in that: first the material of formula ratio is dry mixed in super mixer evenly, mixing machine rotating speed is 400 ~ 500 revs/min, the time of being dry mixed is 5 ~ 10min, then makes through forcing machine extruding pelletization at 170 ~ 220 DEG C.
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| CN106751006A (en) * | 2016-04-17 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of polypropene composition and preparation method thereof |
| CN107841052B (en) * | 2016-09-19 | 2020-03-06 | 中国石油化工股份有限公司 | Polypropylene composition, polypropylene material and application thereof |
| CN109575451A (en) * | 2017-09-29 | 2019-04-05 | 中国石化扬子石油化工有限公司 | A kind of toothbrush handle polypropylene material and preparation method thereof |
| CN109575426A (en) * | 2017-09-29 | 2019-04-05 | 中国石化扬子石油化工有限公司 | A kind of toothbrush handle polypropylene material and preparation method thereof |
| CN109206821B (en) * | 2018-08-31 | 2021-12-07 | 柏力开米复合塑料(昆山)有限公司 | Polypropylene composite material and preparation method thereof |
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