CN103665570A - Ultra-low temperature toughened polypropylene composition - Google Patents
Ultra-low temperature toughened polypropylene composition Download PDFInfo
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- CN103665570A CN103665570A CN201310610333.1A CN201310610333A CN103665570A CN 103665570 A CN103665570 A CN 103665570A CN 201310610333 A CN201310610333 A CN 201310610333A CN 103665570 A CN103665570 A CN 103665570A
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- polypropene composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses an ultra-low temperature toughened polypropylene composition. The ultra-low temperature toughened polypropylene composition comprises the following components: 40-80% of polypropylene, 15-30% of a toughening agent and 5-30% of a filling reinforcing agent. According to the invention, elastic bodies with low density, low melt index and low glass transition temperature are selected and used to be in crosslinking with dicumyl peroxide (DCP) to obtain XPOE used as the toughening agent. The prepared polypropylene composition has good low temperature impact toughness, particularly, the multi-shaft low temperature impact strength, and also has good rigidity. An automobile upholstery prepared by using the ultra-low temperature toughened polypropylene composition can meet the automobile industrial safety and appearance use requirements, and can pass an ultra-low temperature (-40 DEG C) multi-shaft impact test.
Description
Technical field
The present invention relates to a kind of polypropene composition, be specifically related to a kind of ultralow-temperature flexibility polypropene composition and preparation method thereof.
Background technology
Polypropylene PP is a kind of broad-spectrum general-purpose plastics, by propylene monomer, is polymerized, and its fusing point is 165 ~ 175 ℃, belongs to hemicrystalline plastics.Acrylic plastering has the features such as light, the easy processing of quality, becomes maximum, the with the fastest developing speed kind of consumption in automotive plastic.But the resistance to low temperature of polypropylene material is poor, and rigidity is low, can not meet requirement and the standard of automotive upholstery.Inside gadget comprises dashboard, auxiliary fasia console, A, B and C column, glove box, door-plate, trunk plate etc.
In order to improve polyacrylic low-temperature flexibility and rigidity, the way conventionally adopting is to add elastomerics to improve low temperature impact properties, adds the rigidity that mineral filler improves material.CN101550252A discloses a kind of by polypropylene, polyethylene, ethylenic copolymer rubber, the polypropene composition with good low temperature properties and good appearance that talcum powder and oxidation inhibitor form; EP 0794222-A1 has announced and has comprised polypropylene, containing the thermoplastic resin composition of cinnamic elastomerics and talcum, has wherein reported the balance of acceptable toughness and rigidity; WO03/07076511A1 adopts HDPE and ethene-hexene or ethylene-butene copolymer Toughened PP.
Yet in above-mentioned document still there is the imperfect defect of over-all properties of low-temperature impact toughness and rigidity in disclosed polypropylene composite material.And, these utilizations be that socle girder or simply supported beam notched Izod impact strength are evaluated low temperature impact properties, the multiaxis low temperature impact strength of material is not evaluated, although notched Izod impact strength can be evaluated low temperature impact properties to a certain extent, can not meet the evaluation of the safety performance of automobile.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of ultralow-temperature flexibility polypropene composition, and said composition has good low-temperature impact toughness, multiaxis low temperature impact strength especially, and keep good rigidity.
Another object of the present invention is to provide a kind of preparation method of above-mentioned ultralow-temperature flexibility polypropene composition.
The present invention is achieved through the following technical solutions:
A ultralow-temperature flexibility polypropene composition, by mass percentage, comprises following component:
Polypropylene: 40-80%
Toughner: 15-30%
Fill toughener: 5-30%;
Described toughner, by mass percentage, comprises following component:
Ethylene-butene copolymer and/or ethylene-octene copolymer 97%-99%
Oxidation diisopropylbenzene(DIPB) 1%-3%.
The toughner that the present invention selects is XPOE, and its preparation method is obtained with oxidation diisopropylbenzene(DIPB) (DCP) is crosslinked by POE.In XPOE, POE mass percent is 97%-99%, and DCP mass percent is 1%-3%.Described POE is that low glass transfers ethylene-butene copolymer and/or the ethylene-octene copolymer that temperature, low density eutectic refer to, its second-order transition temperature <-55 ℃, and density is 0.850-0.8700g/cm
3, melt mass flow rate is 0.2-2g/10min(190 ℃/2.16kg).
Thereby the XPOE that the present invention selects can strengthen the interface interaction of POE and PP matrix and further improve shock strength and rigidity.
And adopt low glass transfer ethylene-butene copolymer that temperature, low density, eutectic refer to and/or ethylene-octene copolymer be because: propene polymer is at room temperature toughness material, under mechanical stress only in Materials Fracture product generation viscous deformation.Yet at the temperature reducing, propene polymer shows brittle rupture.Employing has the polyolefin elastomer of extremely low second-order transition temperature, at lower temperature, polyolefin elastomer in blend still can keep good deformation and motor capacity, still can cause a large amount of crazings and shear zone to polypropylene matrix, thereby improves the low-temperature flexibility of blend.
Described filling toughener is for take the talcum powder master batch that POE is carrier.
The preparation method of described talcum powder master batch comprises the steps: by mass percentage, get the POE of 10-30% and the talcum powder of 70-90% and mix at 170-250 ℃ of temperature, granulation, cooling after and get final product.
Talcum powder is prepared into master batch, and what can make that talcum powder disperses in blend is more even, also contributes to reduce dust, improves Working environment.
Described polypropylene is propylene copolymer, and its melt flow rate (MFR) is 20-60g/10min under 230 ℃, 2.16kg condition, socle girder notched Izod impact strength Izod>=15 KJ/m
2.
Ultralow-temperature flexibility polypropene composition of the present invention also comprises 0.1-4%(mass percent) other additive, described other additives are one or more the mixing in thermo-stabilizer, photostabilizer, processing aid or pigment.Because the present invention is automotive trim polypropene composition, can to above-mentioned additive, use separately according to the structure of different automotive trims, technical requirements etc., or compound use.
Thermo-stabilizer can improve the heat aging property of material in processing and use procedure, conventionally can be selected from more than one in phenols, phosphorous acid esters, monothioester class.
Photostabilizer can improve material light aging resisting property in use, can be hindered amines or UV light absorber.
Processing aid is more than one in low molecule ester class stearic acid, metallic soap (Cast, Znst), stearic acid complex ester or amides (erucicamide).
The preparation method of ultralow-temperature flexibility polypropene composition of the present invention, comprises the following steps:
After each raw material is mixed, join in twin screw extruder, melting mixing at 180-230 ℃, then granulation, cooling, obtains.
The present invention compared with prior art, has following beneficial effect:
1) the present invention selects low density, eutectic refer to and second-order transition temperature is low elastomerics and oxidation diisopropylbenzene(DIPB) (DCP) crosslinked and obtain XPOE, XPOE can strengthen the interface interaction of POE and PP matrix and make more evenly refinement of the dispersion of elastomerics in polypropylene matrix, improves its low temperature impact properties;
2) the present invention uses and take the talcum powder master batch that POE is carrier, can reduce Working environment dust, has also guaranteed material simultaneously
There is good rigidity.
3) polypropene composition that prepared by the present invention has good low-temperature impact toughness, especially multiaxis low temperature impact strength, and keep good rigidity, the automotive upholstery that uses product of the present invention to prepare, automotive industry safety and outward appearance service requirements not only can be met, and very low temperature (40 ℃) multiaxis Impact Test can be passed through.
Embodiment
Below by embodiment, further illustrate the present invention, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
embodiment 1-5, comparative example 1-5
A polypropene composition, its preparation method comprises the following steps:
(1) get 20% POE and mix at 170 ℃ with 80% talcum powder, granulation, obtain take the talcum powder master batch that POE is carrier after cooling; Described per-cent accounts for the per-cent of raw material total mass for each raw material;
(2) composition of raw materials of polypropene composition is in Table 1, after each raw material is mixed, join in twin screw extruder, and melting mixing at 230 ℃, then granulation, cooling, obtains polypropene composition.
The toughner that embodiment adopts from comparative example is different, and its specific performance parameter is in Table 2.
The polypropene composition that embodiment and comparative example obtain adopts following methods to test its correlated performance:
(1) modulus in flexure: press ISO178 test, speed is 2mm/min;
(2) socle girder notched Izod impact strength: press ISO180 test;
(3) multiaxis shock strength: press ASTM D3763 test, impact velocity is 6.6m/s, and impact head diameter is 12.7mm, and supporting cup diameter is 76.2mm.
The performance perameter that test obtains is in Table 3.
the composition of raw materials of the polypropene composition of table 1 embodiment and comparative example (by mass percentage)
the performance index of the toughner that table 2 embodiment and comparative example adopt
the performance test results of the polypropene composition of table 3 embodiment and comparative example
the performance test results of the polypropene composition of continued 3 embodiment and comparative example
By product test result, can be found out:
Compare with embodiment 1, comparative example 1 is selected the elastomerics of high molten finger, high-vitrification invert point, although its normal temperature performance and embodiment 1 are similar, its low temperature multiaxis impacts for brittle fracture.
Comparative example 2 is compared with embodiment 2, and what comparative example 2 was selected is the elastomerics of high-density, high-vitrification invert point, and its low temperature multiaxial performance is similarly brittle fracture.
Comparative example 3 is compared with embodiment 3, although comparative example 3 selects, is the elastomerics that low density, eutectic refer to, crosslinked with oxidation diisopropylbenzene(DIPB) (DCP), causes its interface binding power also poor, so its low temperature multiaxis impacts the percent of pass that also only has 30%.
Comparative example 4 is compared with embodiment 4, in comparative example 4 with the content of elastomer crosslinked oxidation diisopropylbenzene(DIPB) (DCP) higher than 3%, can see, its normal temperature impacts and low-temperature impact has decline to a certain degree, and its low temperature multiaxis impacts the percent of pass that also only has 50%.This is because a certain amount of DCP can make material form network structure as linking agent, and when DCP content is too high, the density of cross-linking set improves, cause material excessively crosslinked, molecular chain length between cross-linking set shortens, and has destroyed crystallizing field, on the contrary the mechanical property of material is brought to disadvantageous effect.
Comparative example 5 is compared with embodiment 5, what in comparative example 5, adopt is talcum powder (24 parts of talcum powder are the same with the contained talcum powder weight in 30 parts of talcum master batches in embodiment 5), can see, use talcum master batch, the toughness of composition and rigidity are all more excellent than using talcum powder.This is because use talcum powder master batch, can make more evenly refinement of elastomerics and the powder dispersion in polypropylene matrix.
And embodiment is used the elastomerics that low density, eutectic refer to, second-order transition temperature is low be cross-linked with oxidation diisopropylbenzene(DIPB) (DCP) and obtain XPOE as toughner, XPOE can strengthen the interface interaction of POE and PP matrix, the polypropene composition of preparation has good low-temperature impact toughness, especially multiaxis low temperature impact strength, can pass through very low temperature (40 ℃) multiaxis Impact Test, and keep good rigidity.
Claims (8)
1. a ultralow-temperature flexibility polypropene composition, is characterized in that: by mass percentage, comprise following component:
Polypropylene: 40-80%
Toughner: 15-30%
Fill toughener: 5-30%;
Described toughner, by mass percentage, comprises following component:
Ethylene-butene copolymer and/or ethylene-octene copolymer 97%-99%
Oxidation diisopropylbenzene(DIPB) 1%-3%;
Wherein, the second-order transition temperature <-55 ℃ of described ethylene-butene copolymer and/or ethylene-octene copolymer, density is 0.850-0.8700g/cm
3, melt mass flow rate is 0.2-2g/10min under 190 ℃, 2.16kg condition.
2. ultralow-temperature flexibility polypropene composition according to claim 1, is characterized in that: described filling toughener is for take the talcum powder master batch that POE is carrier.
3. ultralow-temperature flexibility polypropene composition according to claim 2, it is characterized in that: the preparation method of described talcum powder master batch comprises the steps: by mass percentage, get the POE of 10-30% and the talcum powder of 70-90% and mix at 170-250 ℃ of temperature, granulation, cooling after and get final product.
4. ultralow-temperature flexibility polypropene composition according to claim 1, it is characterized in that: described polypropylene is propylene copolymer, its melt flow rate (MFR) is 20-60g/10min under 230 ℃, 2.16kg condition, socle girder notched Izod impact strength Izod>=15 KJ/m
2.
5. ultralow-temperature flexibility polypropene composition according to claim 1, is characterized in that: other additive that also comprises 0.1-4%.
6. ultralow-temperature flexibility polypropene composition according to claim 5, is characterized in that: described other additives are one or more the mixing in thermo-stabilizer, photostabilizer, processing aid or pigment.
7. ultralow-temperature flexibility polypropene composition according to claim 6, is characterized in that: described thermo-stabilizer is more than one in phenols, phosphorous acid esters, monothioester class; Described photostabilizer is one or more the mixing in hindered amines or UV light absorber; Described processing aid is more than one in low molecule ester class stearic acid, metallic soap, stearic acid complex ester or amides.
8. the preparation method of the ultralow-temperature flexibility polypropene composition described in claim 1 ~ 7 any one, is characterized in that: comprise the following steps:
After each raw material is mixed, join in twin screw extruder, melting mixing at 180-230 ℃, then granulation, cooling, obtains.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103951876A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Environment-friendly type high-toughness and flame retardation polypropylene material as well as preparation method thereof |
| CN103951969A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Polyamide toughening material and preparation method thereof |
| CN104086895A (en) * | 2014-07-03 | 2014-10-08 | 合肥杰事杰新材料股份有限公司 | Ultra-low-temperature resistant composite polypropylene material and preparation method thereof |
| CN105754219A (en) * | 2016-03-31 | 2016-07-13 | 安徽纽麦特新材料科技股份有限公司 | Polypropylene composite material with high toughness under ultralow temperature and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951876A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Environment-friendly type high-toughness and flame retardation polypropylene material as well as preparation method thereof |
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| CN104086895A (en) * | 2014-07-03 | 2014-10-08 | 合肥杰事杰新材料股份有限公司 | Ultra-low-temperature resistant composite polypropylene material and preparation method thereof |
| CN104086895B (en) * | 2014-07-03 | 2019-03-29 | 合肥杰事杰新材料股份有限公司 | A kind of super low-temperature resistant PP composite material and preparation method thereof |
| CN105754219A (en) * | 2016-03-31 | 2016-07-13 | 安徽纽麦特新材料科技股份有限公司 | Polypropylene composite material with high toughness under ultralow temperature and preparation method and application thereof |
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