CN102952341A - 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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- CN102952341A CN102952341A CN2011102520914A CN201110252091A CN102952341A CN 102952341 A CN102952341 A CN 102952341A CN 2011102520914 A CN2011102520914 A CN 2011102520914A CN 201110252091 A CN201110252091 A CN 201110252091A CN 102952341 A CN102952341 A CN 102952341A
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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 the 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
Polypropylene because have that density is little, good heat resistance, intensity are high, have the advantages such as good resistance to water soak, antiacid caustic corrosion, resist dissolution, have developed into the second largest general-purpose plastics except polyethylene at present.Modified polypropene is exactly that various properties-correcting agent further improve and the expansion Properties of Polypropylene by adding, and makes it obtain to use widely, can be used for each large field such as automobile, household electrical appliances, daily necessities.But the matrix material that polypropylene itself and various additives can make preparation usually makes its feature of environmental protection not reach service requirements with larger smell.Along with the fast development of each industrial circle and the day by day raising of people's living standard, polypropylene modified material is proposed more, higher requirement, except will improving mechanical property, fluidity of molten, also more and more higher to the smell requirement of material.And polyacrylic rigidity and toughness is mutually restriction, and the 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.
The modified polypropylene material that has simultaneously again low smell with regard to how obtaining high-performance also has the research of some patents and document to report.
The people such as Weng Yonghua have proposed a kind of low smell, low-volatile polypropylene composite material in patent CN 1727389A, it is the performance that realizes its low smell, low-volatile by the way that adopts Kiselgel A, employed polypropylene is a kind of or its combination in high crystallization homo-polypropylene or the block copolymerization polypropylene, 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 Zaichun have proposed a kind of low modified polypropylene composite material that distributes and preparation method thereof in patent CN 101817953A, be to share by three kinds of mixtures in clay, wilkinite, porous silica, activated alumina or the molecular sieve that agent reduces the matrix material smell as odor adsorption.
Kim, the people such as Hee-Soo (are published in Journal of Applied Polymer Science (2008), 110 (5): 3247-3255) studied zeolite type and content to the impact of natural powder filling polypropylene composite material mechanical property, thermal characteristics, smell and volatile organic matter VOC discharging.The result shows that zeolite can effectively reduce smell and the VOC quantity discharged that the nature powder is filled thermoplastic polymer composite material, does not affect mechanical property and the thermal characteristics of material simultaneously.
The people such as Zhou Yinghui have proposed a kind of high-performance low-odour polypropylene dedicated for automobile dashboard and preparation method thereof in patent CN 1840576A, its practical smell properties-correcting agent is inorganic mealy molecular sieve, when the modulus in flexure of material under 23 ℃ reached 2400MPa, the socle girder notched Izod impact strength still can reach 42kJ/m
2More than; The smell rank can reach more than 6 grades of GM standard.
Although the system mechanical property defectiveness that above-mentioned research has is low such as rigidity high resistance to impact shock; The smell of the raw material of the employing that has own is large, carries it into composite system, and the system smell of making can't reach lower level.
Summary of the invention
The purpose 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 basis 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 smell inhibitor that can effectively reduce the composition material smell, prepare a kind of cheaply polypropene composition of low smell, high impact properties.
The strong and unyielding low-odor polypropylene ene compositions of height of the present invention, made by 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: with 100 parts in Co-polypropylene powder; 31,14/,330 0.4 parts of composite antioxidants; 0.1 part of acid-acceptor Cast; 0.1 part of lubricants GMS after fully mixing, is made through the twin screw extruder extruding pelletization.It is 170 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 210 ℃ that forcing machine is respectively distinguished temperature, and screw speed is 200～300rpm, and granulation screw adopts and vacuumizes vacuum tightness 0.3MPa.Co-polypropylene powder degree of isotacticity is more than 95%, in every kg polypropylene catalyst residue less than 0.02g, its comonomer ethylene content 6～13mol%, preferred 11～13mol%; Composite antioxidant 3114/330,3114 and 330 both composite mass ratioes are 1.0.The low smell High Impact Polypropylene resin melt mass flow rate of preparing is 7～30g/10min, preferred 8～11g/10min, why to select low smell High Impact Polypropylene be the rigidity that provides for composition and shock resistance, and reduce as far as possible and bring smell into.
Described amount of talc is 18～25 parts, and particle diameter is 1000～5000 orders, preferred 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 smell inhibitor in the composition, smell that each component of active adsorption has and that in processing, use, produce, and also white carbon black self color and luster is close with polypropylene, can make the composition hue preserving better, and be conducive to be deployed into other color.
Preferred 0.7～0.8 part of described composite antioxidant consumption, composite antioxidant are the primary antioxidant of high-melting-point, low-volatile and the mixture of auxiliary anti-oxidant, and the fusing point of primary antioxidant and auxiliary anti-oxidant requires to be 218-224 ℃, fugitive constituent≤0.1%.The preferred primary antioxidant 3114 of the present invention, chemical name are 1,3,5-three (3, the 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-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene.Both compound proportions are 1: 1～2, preferred 1: 1～1.5.
The preparation method of the strong and unyielding low-odor polypropylene ene compositions of height of the present invention is as follows: the material with formula ratio is dry mixed in super mixer evenly first, the mixing machine rotating speed is 400～500 rev/mins, the time of being dry mixed is 5～10min, makes at 170～220 ℃ of lower extruding pelletizations through forcing machine again.
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, uses the high efficiency composition oxidation inhibitor of high-melting-point, low-volatile, low smell, adopts simultaneously again efficient smell inhibitor, and prepared composition can reach lower oder levels;
(2) to adopt the acrylic resin of high-impact be raw material in the present invention, even add the mineral filler of high level such 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) fields such as the composition of the present invention preparation automobile that can be used for mechanical property and the feature of environmental protection are had relatively high expectations, household electrical appliances promote this art progress, have 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, and I type batten, draw speed are 50mm/min;
3, the socle girder notched Izod impact strength is undertaken by GB/T 1843-2008, and wherein low-temperature process is-20 ℃ of placements 2 hours, and the normal temperature treating processes is 23 ℃ and placed 24 hours;
4, bending elastic modulus, flexural strength are undertaken by GB/T 9341-2008;
5, the smell property testing carries out according to the method for germany volkswagen standard P V3900, and the judgment criteria of its oder levels is: be difficult for feeling for grade 1, can feel but pungent for grade 2, can obviously feel but pungent for grade 3, pungent for class 4, very pungent for class 5, can not stand and be class 6.
Embodiment 1～6
The preparation method of low smell impact polypropylene is as follows: with 100 parts in Co-polypropylene powder; 3114/3300.4 part of composite antioxidant; 0.1 part of acid-acceptor Cast; 0.1 part of lubricants GMS after fully mixing, is made through the twin screw extruder extruding pelletization.It is 170 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 210 ℃ that forcing machine is respectively distinguished temperature, and screw speed is 250 ± 50rpm, and granulation screw adopts and vacuumizes vacuum tightness 0.3 MPa.Co-polypropylene powder degree of isotacticity 95%, catalyst residue is less than 0.02g in every kg polypropylene, and composite antioxidant 3114/330,3114 and 330 both composite mass ratioes are 1.0.
Component, proportioning and the performance index of the high strong and unyielding low-odor polypropylene ene compositions described in the embodiment 1～6 are as shown in table 1.
High strong and unyielding low odor polypropylene preparation method of composition described in the embodiment 1～6 is as follows: take by weighing each raw material by formula ratio, in high-speed mixer, mix 7 ± 1 minutes, the mixing machine rotating speed is 450 ± 50 rev/mins, after the discharging in twin screw extruder extruding pelletization, it is 170 ℃, 180 ℃, 190 ℃, 200 ℃, 220 ℃, 210 ℃ that forcing machine is respectively distinguished temperature, and screw speed is 200～300rpm.
Table 1 embodiment 1～6 component, proportioning and performance index table
Comparative Examples 1～2
The component of the polypropene composition described in the Comparative Examples 1～2, proportioning and performance index are as shown in table 2.
The preparation method of Comparative Examples 1～2 such as embodiment 1～6.
Table 2 Comparative Examples component, proportioning and performance index table
| Form and performance | Comparative Examples 1 | Comparative Examples 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 |
| The fracture norminal strain, % | 65 | 83 |
| Stress in bending | 30.6 | 29.8 |
| Bending elastic modulus, MPa | 1950 | 1877 |
| 23 ℃ of socle girder notched Izod impact strength, kJ/m 2 | 12.3 | 13.9 |
| Socle girder notched Izod impact strength-20 ℃, kJ/m 2 | 3.4 | 3.7 |
| The load deformation temperature, ℃ | 113 | 110 |
| Oder levels | 4.0 | 3.5 |
From embodiment and Comparative Examples performance test results, adopt in the situation of plain polypropylene, common oxidation inhibitor, when identical POE consumption, the toughness of Comparative Examples is lower, smell is larger, and rigid phase is worked as; In the situation that adopts plain polypropylene, common oxidation inhibitor, when adopting the white carbon black of same amount, the oder levels of Comparative Examples decreases, but still is higher than embodiment.
Claims (10)
1. one kind high strong and unyielding low-odor polypropylene ene compositions is characterized in that being made by the raw material of following parts by weight:
2. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1, it is characterized in that described impact polypropylene is low smell High Impact Polypropylene resin, its comonomer ethylene content is 6～13mol%, and its melt mass flow rate is 7～30g/10min.
3. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 2 is characterized in that described low smell High Impact Polypropylene resin, and its comonomer ethylene content is 11～13mol%, and its melt mass flow rate is 8～11g/10min.
4. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1 is characterized in that described amount of talc is 18～25 parts, and particle diameter is 1000～5000 orders.
5. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 4 is characterized in that described talcous particle diameter is 1000～2000 orders.
6. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1 is characterized in that described toughner is POE, and consumption is 7～10 parts.
7. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1 is characterized in that described white carbon black is 3～5 parts, and median size is 1000～5000 orders, and BET method specific surface area is 50～500m
2/ g.
8. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 7 is characterized in that described white carbon black median size is 3000～5000 orders.
9. the strong and unyielding low-odor polypropylene ene compositions of height according to claim 1 is characterized in that described composite antioxidant is the mixture of primary antioxidant 3114 and auxiliary anti-oxidant 330, and its composite mass ratio is 1: 1～2, and consumption is 0.7～0.8 part.
10. the preparation method of the strong and unyielding low-odor polypropylene ene compositions of height claimed in claim 1, it is characterized in that: the material with formula ratio is dry mixed in super mixer evenly first, the mixing machine rotating speed is 400～500 rev/mins, the time of being dry mixed is 5～10min, makes at 170～220 ℃ of lower extruding pelletizations through forcing machine again.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107841052A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of polypropene composition and polypropylene material and its application |
| CN109206821A (en) * | 2018-08-31 | 2019-01-15 | 柏力开米复合塑料(昆山)有限公司 | A kind of PP composite 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 |
| 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 |
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| US20050048245A1 (en) * | 2003-09-01 | 2005-03-03 | Larry Mullinax | High-strength, low-cost, recyclable backing for fabrics and method for making same |
| CN1840576A (en) * | 2005-04-01 | 2006-10-04 | 上海金发科技发展有限公司 | High-performance low-odour polypropylene dedicated for automobile dashboard and method for preparing same |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050048245A1 (en) * | 2003-09-01 | 2005-03-03 | Larry Mullinax | High-strength, low-cost, recyclable backing for fabrics and method for making same |
| CN1840576A (en) * | 2005-04-01 | 2006-10-04 | 上海金发科技发展有限公司 | High-performance low-odour polypropylene dedicated for automobile dashboard and method for preparing same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107841052A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of polypropene composition and polypropylene material and its application |
| 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 |
| 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 |
| CN109206821A (en) * | 2018-08-31 | 2019-01-15 | 柏力开米复合塑料(昆山)有限公司 | A kind of PP composite 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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