CN102276922A - Polypropylene composition with low linear expansion coefficient and preparation method thereof - Google Patents
Polypropylene composition with low linear expansion coefficient and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polypropylene composition with a low linear expansion coefficient and a preparation method thereof. The polypropylene composition comprises the following components in percentage by weight: 40 to 70 percent of polypropylene resin, 10 to 30 percent of elastomer, 5 to 30 percent of filler with a high aspect ratio, 0 to 20 percent of other inorganic fillers, 0.5 to 10 percent of compatilizer and 0.05 to 5 percent of other additives. In the polypropylene composition, the inorganic filler with an aspect ratio (HAR) is filled to enhance the polypropylene composition or the inorganic filler with the HAR and the ordinary inorganic filler are combined and filled to enhance the polypropylene composition, and the compatilizer is added to be compounded and modified, so that a plastic part formed by the injection molding of the polypropylene composition has the low linear expansion coefficient, has high dimensional stability in the circulation of high and low temperature, and has the expansion coefficients which are equal approximately along the flow direction (FD or MD) of injection molding and the transverse direction (TD). The preparation method is simple and practical, and the use range of modified polypropylene materials in fields of automobiles, home appliances, mechanical industry and the like is enlarged.
Description
Technical field
The present invention relates to a kind of polypropene composition, the polypropene composition of particularly a kind of low coefficient of linear expansion (CLTE) belongs to the modified polypropene technical field.
Background technology
Acrylic resin has that range of product is many, work range is wide, density is low, chemical resistance is good, environmental stress resistance be full of cracks performance is good, can reduce noise, the product integration is good, can onlinely dye, advantages such as utilization, low price more capable of circulation.Yet polypropylene material itself also exists some defectives such as coefficient of linear expansion is bigger, the size instability, thus limited its range of application, be difficult to be widely used in some performance requriementss higher field, especially automotive industry.
Existing automotive industry requires the fit-up gap between the different products as far as possible little, and dimensional stabilizing, and this just requires the coefficient of linear expansion of polypropylene material lower.Also require to have lower linear expansivity when modified polypropylene material is used for fields such as electric appliance casing and machine tool in addition.People adopt some mineral fillers of interpolation and elastomeric mode to reduce the linear expansivity of polypropylene material usually for this reason, though this method can reduce material linear expansivity of (FD or MD) on the melt flow direction on a kind of degree, but this polypropylene multicomponent system is owing to itself exist bigger anisotropy, therefore Injection moulded part tends to produce huge difference at the coefficient of linear expansion of FD and TD, as material be 80 μ m/m/ ℃ at the coefficient of linear expansion of FD direction, and the TD direction is 170 μ m/m/ ℃, be difficult to satisfy the design requirement of high-grade automotive part, and coefficient of linear expansion is excessive and the excessive product appearance quality that not only has a strong impact on of difference on FD and TD direction, even also can bring potential safety hazard, therefore it is just extremely urgent to solve the excessive defect problem of big and FD of polypropylene material coefficient of linear expansion and TD direction difference.
In order to satisfy the requirement of automotive part, people have proposed to reduce the method for coefficient of linear expansion.CN101624459A discloses the composition of the acrylic resin with low-shrinkage and dimensional stability.This invention provides a kind of have relative higher rigidity and shock resistance and the relatively low molding shrinkage and the polypropene composition of coefficient of linear expansion.CN1834145A discloses polypropylene composite material for automobile bumper and preparation method, and this material has high polarity and low coefficient of linear expansion.But these two patents only are to have reported that material has lower linear expansivity, yet but specifically do not mention the coefficient of linear expansion situation of material, and neither reduce polyacrylic linear expansivity by adding high length-diameter ratio (HAR) mineral filler at FD and TD.
Chinese patent CN200710047775.4 discloses a kind of preparation method of low-contraction high-fluidity high-toughness polypropylene, and each component is: (1) high-flowability polypropylene, (2) thermoplastic polyolefin elastomer, (3) toughner, (4) mineral filler, (6) oxidation inhibitor, (7) weather resisting agent, (8) processing aid, its advantage is that shock strength height and injection moulding shrinking percentage are low, but its weak point is, weighting material is assembled in polypropylene easily, thereby causes its filling properties bad.
Summary of the invention
The object of the present invention is to provide and a kind ofly be used for injection moulding and have low and all to polypropene composition of coefficient of linear expansion and preparation method thereof.
To achieve these goals, technical scheme of the present invention is a kind of polypropene composition that low coefficient of linear expansion is provided, and it is characterized in that, comprises following component by weight percentage:
Acrylic resin 40 ~ 70%;
Elastomerics 10 ~ 30%;
High length-diameter ratio mineral filler 5 ~ 30%;
Other mineral fillers 0 ~ 20%;
Compatilizer 0.5 ~ 10%;
Other additives 0.05 ~ 5%.
Above-mentioned acrylic resin can be homo-polypropylene or Co-polypropylene or by being wherein several blends of forming; Polyacrylic melt flow rate (MFR) (MFR) is 5 ~ 60g/10min, wherein the socle girder notched Izod impact strength 〉=0.5KJ/m of homo-polypropylene
2(23 ℃), the socle girder notched Izod impact strength 〉=5KJ/m of Co-polypropylene
2That (23 ℃), Co-polypropylene can be selected is random, block or branch shape multipolymer.Acrylic resin can adopt cationic coordinate polymerization, the coordination polymerization of Ziegler-Natta negative ion or with metallocene catalyst synthetic polypropylene.
Above-mentioned elastomerics is an alpha-olefin copolymer, and elastomeric selection can be wherein one or more; The carbonatoms of alhpa olefin is 2 ~ 10, and comparatively the carbonatoms of ideal alhpa olefin is 2 ~ 4, and elastomerics density is 0.850 ~ 0.900g/cm
3, comparatively ideal density is 0.850 ~ 0.860g/cm
3, melt mass flow rate is 0.2 ~ 30g/10min(2.16kg, 190 ℃), comparatively the ideal melt mass flow rate is 0.2 ~ 15g/10min(2.16kg, 190 ℃).
Above-mentioned high length-diameter ratio (HAR) mineral filler can be selected one or more the mixture in HAR talcum powder, HAR wollastonite and the HAR mica powder, its particle diameter≤10 μ m, length-to-diameter ratio 〉=5:1, ideal particle diameter≤6 μ m comparatively, length-to-diameter ratio 〉=15:1.
Above-mentioned other mineral fillers can be selected one or more mixtures in talcum powder, wollastonite, mica powder, barium sulfate and the lime carbonate etc., and its particle size range is 1 ~ 20 μ m, and comparatively the ideal particle size range is 1 ~ 10 μ m.
Above-mentioned compatilizer is the graftomer of polypropylene and maleic anhydride or the graftomer of alpha olefin copolymer and maleic anhydride, its melt flow rate (MFR) is 0.5 ~ 50g/10min(2.16kg, 190 ℃), comparatively the ideal melt flow rate (MFR) is 5 ~ 30g/10min(2.16kg, 190 ℃), maleic anhydride grafting ratio is 0.05 ~ 5%, and comparatively the ideal maleic anhydride grafting ratio is 0.5 ~ 2.5%.
In above-mentioned polypropene composition, can add other different resins according to product requirement, such as adding polyethylene, comprise new LDPE (film grade), linear low density polyethylene or high density polyethylene(HDPE); Can also add other elastomericss such as styrenic elastomerics, comprise SBS, SEBS, also can add the elastomerics of polyvinylidene one class, the addition of these resins is general 〉=1wt%, comparatively ideal addition 〉=5wt%.
The needs that use according to actual product in the composition of the present invention can also add oxidation inhibitor, and oxidation inhibitor is a kind of chemical assistant that can suppress and delay polymer materials oxidation and degraded.Oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, and primary antioxidant can be selected hindered phenol or sulfolipins for use, and auxiliary anti-oxidant can be selected phosphorous acid esters for use.Comparatively ideal oxidation inhibitor has: 2,6-ditertbutylparacresol, 2,4,6-tri-butyl-phenol, 4-methylol-2,6-DI-tert-butylphenol compounds, N-cyclohexyl-N '-phenyl be to diamines, tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester, the selection of oxidation inhibitor one or more in can be above-mentioned, the addition of oxidation inhibitor is generally 0.01% ~ 3% of total weight parts, and comparatively the ideal addition is 0.1% ~ 1%.
In addition can also comprise in shades of colour additive, weather resisting agent, various ester class or the additives such as aliphatics lubricant, nucleator and static inhibitor one or more in the composition of the present invention.The kind of these additives, addition and addition means are prior art, and the content of above-mentioned additive in this composition is generally 0.05 ~ 5% of total weight parts, and comparatively the ideal addition is between 0.1 ~ 2%.
A kind of preparation method of polypropene composition of low coefficient of linear expansion is as follows: after each component is mixed, by the charging of twin screw extruder master spout, the charging of side feeding manner is adopted in the HAR mineral filler, melt extruding temperature is 170 ~ 230 ℃, screw slenderness ratio is not less than 32, the water-cooled tie rod, pelletizing, packing gets final product.
Each composition material adds each composition successively and mixes according to the described weight percentage weighing of prescription (high length-diameter ratio is inorganic fill out except), can adopt the uniform equipment of these mixing of materials, includes but not limited to high-speed mixer, low speed mixer, Banbury mixer; Can adopt single stage method that all components are once dropped on hybrid mode mixes, also can adopt technologies such as two step method or multistep processes that two kinds of components are mixed earlier again mixes with other components, hybrid mode is varied, can be adjusted according to the practical situation of producing.The mixing of materials churning time is 0.5 ~ 60min, and comparatively ideal batch mixing churning time is 1 ~ 15min; After mixed mixing of materials is even, by twin screw extruder or the charging of reciprocating type single screw extrusion machine master spout, the charging of side feeding manner is adopted in the HAR mineral filler, and extruding the melting mixing temperature is 170-230 ℃, and comparatively to extrude the melting mixing temperature be 190-210 ℃ to ideal.Extruding pelletization, water-cooled, air-dry, particle diameter is of a size of 1～5mm in any direction, and comparatively the ideal grain size is 2～3mm, and packing gets final product.
Polypropene composition of low coefficient of linear expansion of the present invention and preparation method thereof, its advantage is:
1. adopt HAR mineral filler and the composite modified polypropene composition material of compatilizer, not only have low coefficient of linear expansion, and linear expansivity has equal tropism;
2. the dimensional stabilizing of Injection moulded part, the fit-up gap is little, can fully satisfy the service requirements of relevant industries such as automobile, household electrical appliances and machinery.
?
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment one
By formula table raw material is weighed up by its usage ratio, be respectively: acrylic resin comprises Co-polypropylene and homo-polypropylene; Elastomerics; The HAR talcum powder; Mica powder; The graft copolymer of compatilizer polypropylene and maleic anhydride; After mixing, add twin screw extruder, the charging of side feeding manner is adopted in the HAR mineral filler, melting mixing under 190 ℃ temperature, and extruding pelletization, water-cooled, air-dry, particle diameter is 2mm, packing gets final product.
Embodiment two
Press the described component batching of table 1, all the other are with embodiment 1.
Embodiment three
Press the described component batching of table 1, all the other are with embodiment 1.
Embodiment four
Press the described component batching of table 1, all the other are with embodiment 1.
Embodiment five
Press the described component batching of table 1, all the other are with embodiment 1.
Embodiment six
Press the described component batching of table 1, all the other are with embodiment 1.
Embodiment seven
Press the described component batching of table 1, all the other are with embodiment 1.
Comparative Examples one
Press the described component batching of table 2, all the other are with embodiment 1.
Comparative Examples two
Press the described component batching of table 2, all the other are with embodiment 1.
Comparative Examples three
Press the described component batching of table 2, all the other are with embodiment 1.
Comparative Examples four
Press the described component batching of table 2, all the other are with embodiment 1.
Comparative Examples five
Press the described component batching of table 2, all the other are with embodiment 1.
The raw material of table 1 polypropene composition and consumption (% by weight percentage)
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Co-polypropylene | 64.4 | 38.4 | 50.4 | 30 | 35 | 40 | 10 |
| Homo-polypropylene | - | 22 | 10 | 10 | 12 | 30 | 30 |
| Elastomerics | 10 | 7 | 16 | 30 | 27 | 18 | 12 |
| The HAR mineral filler | 25 | 20 | 19 | 15 | 11 | 10 | 30 |
| Other mineral fillers | - | 7 | - | - | 5 | - | 17 |
| Compatilizer | - | 5 | 4 | 10 | 8 | 1.9 | - |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | 1 | 0.4 | 0.1 | 0.2 |
| Weather resisting agent | 0.2 | 0.2 | 0.2 | 2 | 0.6 | - | 0.4 |
| Calcium stearate | 0.2 | 0.2 | 0.2 | 2 | 1 | - | 0.4 |
| CLTE(FD) | 58 | 54 | 49 | 43 | 51 | 75 | 49 |
| CLTE(TD) | 74 | 69 | 62 | 57 | 51 | 86 | 58 |
The Comparative Examples raw material of table 2 polypropene composition and consumption (% by weight percentage)
| ? | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 |
| Co-polypropylene | 65.4 | 41.4 | 50.4 | 60 | 48 |
| Homo-polypropylene | - | 20 | 10 | - | 20 |
| Elastomerics | 9 | 8 | 16 | 5 | 2 |
| The HAR mineral filler | - | - | - | - | - |
| Other mineral fillers | 25 | 30 | - | 25 | 28 |
| Compatilizer | - | - | 4 | 8 | 0.6 |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | - | 0.4 |
| Weather resisting agent | 0.2 | 0.2 | 0.2 | 2 | - |
| Calcium stearate | 0.2 | 0.2 | 0.2 | - | 1 |
| CLTE(FD) | 91 | 86 | 117 | 83 | 101 |
| CLTE(TD) | 121 | 114 | 149 | 110 | 129 |
Testing method:
The test of coefficient of linear expansion is carried out according to the ISO11359-2 standard, use the test of thermo-mechanical analysis (TMA) method, sample adopts ISO crooked test batten, need before the test under 90 ℃ of temperature, to anneal 2 hours, Range of measuring temp is-45 ℃～110 ℃, calculate the coefficient of linear expansion (CLTE) in-30 ℃～100 ℃ temperature ranges, each sample need be tested the coefficient of linear expansion on FD and the TD both direction.
Measurement result sees Table 1, table 2 is described, coefficient of linear expansion among the embodiment is all less than the numerical value in the Comparative Examples, thereby as can be seen by the coefficient of linear expansion result of each embodiment and Comparative Examples, the present invention is by adding HAR mineral filler and the compound reinforced modifier of compatilizer, overcome the polypropene composition coefficient of linear expansion for preparing in the prior art big and uneven to shortcoming, the size of Injection moulded part under high low temperature cycling condition is more stable, has enlarged the range of application in the material field of polypropene composition.
Claims (7)
1. the polypropene composition of a low coefficient of linear expansion is characterized in that, comprises following component by weight percentage:
Acrylic resin 40 ~ 70%;
Elastomerics 10 ~ 30%;
High length-diameter ratio mineral filler 5 ~ 30%;
Other mineral fillers 0 ~ 20%;
Compatilizer 0.5 ~ 10%;
Other additives 0.05 ~ 5%.
2. according to the described polypropene composition of claim 1, it is characterized in that: described acrylic resin is the blend of homopolymerization or Co-polypropylene resin or its several compositions, its melt mass flow rate is 5 ~ 60g/10min, wherein the socle girder notched Izod impact strength 〉=0.5KJ/m of homo-polypropylene
2, the socle girder notched Izod impact strength 〉=5KJ/m of Co-polypropylene
2, it is measured all under 23 ℃ of conditions.
3. according to the described polypropene composition of claim 1, it is characterized in that: described elastomerics is an alpha olefin copolymer, used elastomerics can be wherein one or more, the carbonatoms of alhpa olefin is 2 ~ 10, its density is 0.850 ~ 0.900g/cm
3, melt mass flow rate is 0.2-50g/10min down for 190 ℃ in temperature.
4. according to the described polypropene composition of claim 1, it is characterized in that: described high length-diameter ratio mineral filler is one or more the mixture in HAR talcum powder, HAR wollastonite and the HAR mica powder, its particle diameter≤10 μ m, length-to-diameter ratio 〉=5:1.
5. according to the described polypropene composition of claim 1, it is characterized in that: described other mineral fillers are one or more the mixture in talcum powder, wollastonite, mica powder, barium sulfate and the lime carbonate, and its particle size range is 1 ~ 20 μ m.
6. according to the described polypropene composition of claim 1, it is characterized in that: described compatilizer is the graftomer of polypropylene and maleic anhydride or the graftomer of alpha olefin copolymer and maleic anhydride, its melt flow rate (MFR) is 0.5 ~ 50g/10min, and maleic anhydride grafting ratio is 0.05% ~ 5%.
7. the preparation method who prepares described each polypropene composition of claim 1 ~ 6, after comprising the steps: each component mixed, by the charging of twin screw extruder master spout, the charging of side feeding manner is adopted in the HAR mineral filler, melt extruding temperature is 170 ~ 230 ℃, and screw slenderness ratio is not less than 32, the water-cooled tie rod, pelletizing, packing gets final product.
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Cited By (9)
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| CN102532701A (en) * | 2011-12-16 | 2012-07-04 | 金发科技股份有限公司 | Low-warp creep-resistant polypropylene composite as well as preparation method and application thereof |
| CN103102592A (en) * | 2013-02-04 | 2013-05-15 | 北京海科华昌新材料技术有限公司 | Modified polypropylene material for automotive bumper and preparation method thereof |
| CN104558840A (en) * | 2014-12-24 | 2015-04-29 | 上海金发科技发展有限公司 | Injection-molded type TPO (thermoplastic polyolefin) compound for sound-insulating pads for automobiles as well as preparation method of compound |
| CN106147034A (en) * | 2016-06-30 | 2016-11-23 | 中广核俊尔新材料有限公司 | A kind of PP composite material of low linear expansion coefficient and its preparation method and application |
| CN106750542A (en) * | 2016-12-08 | 2017-05-31 | 姚均甫 | A kind of high activity wollastonite raw powder's production technology |
| CN109796681A (en) * | 2018-12-06 | 2019-05-24 | 宁波泰甬汽车零部件有限公司 | High-impact low linear expansion coefficient modified polypropylene material, preparation method and automobile plastic tail-gate |
| CN110218394A (en) * | 2019-05-24 | 2019-09-10 | 骆驼集团塑胶制品有限公司 | A kind of electrolyte resistance polypropylene modified material of low temperature ultra-toughness and preparation method thereof |
| CN112759833A (en) * | 2020-12-29 | 2021-05-07 | 金发科技股份有限公司 | High-rigidity high-toughness polypropylene composite material and preparation method and application thereof |
| CN113861566A (en) * | 2021-09-18 | 2021-12-31 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
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| CN104558840A (en) * | 2014-12-24 | 2015-04-29 | 上海金发科技发展有限公司 | Injection-molded type TPO (thermoplastic polyolefin) compound for sound-insulating pads for automobiles as well as preparation method of compound |
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| CN110218394A (en) * | 2019-05-24 | 2019-09-10 | 骆驼集团塑胶制品有限公司 | A kind of electrolyte resistance polypropylene modified material of low temperature ultra-toughness and preparation method thereof |
| CN112759833A (en) * | 2020-12-29 | 2021-05-07 | 金发科技股份有限公司 | High-rigidity high-toughness polypropylene composite material and preparation method and application thereof |
| CN113861566A (en) * | 2021-09-18 | 2021-12-31 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
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