CN105273301A - Low-shrinkage polypropylene composite material and preparation method thereof - Google Patents
Low-shrinkage polypropylene composite material and preparation method thereof Download PDFInfo
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- CN105273301A CN105273301A CN201410251238.1A CN201410251238A CN105273301A CN 105273301 A CN105273301 A CN 105273301A CN 201410251238 A CN201410251238 A CN 201410251238A CN 105273301 A CN105273301 A CN 105273301A
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Abstract
The invention belongs to the technical field of plastic processing, and concretely relates to a low-shrinkage polypropylene composite material. The material is prepared from the following raw materials in parts by mass: 59.5-89.95 parts of polypropylene resin, 10-35 parts of metallocene linear low density polyethylene, 1-5 parts of a flexibilizer and 0.05-0.5 part of talcum powder. The composite material is prepared from a mixture of metallocene linear low density polyethylene, the flexibilizer and talcum powder and the low-shrinkage polypropylene through blending modification, the polypropylene large shrinkage problem is solved, operation is simple, and the composite is widely applicable to direct injection molding production of high-grade parts with relatively high requirement on shrinkage and applied to re-modified base resin. The invention also provides a preparation method for the composite material, and the preparation method is reasonable in technology.
Description
Technical field
The invention belongs to technical field of plastic, be specifically related to a kind of low-shrinkage polypropylene composite material and preparation method thereof.
Background technology
Polypropylene has good mechanical property, nontoxic, relative density is low, heat-resisting, chemicals-resistant, be easy to the advantages such as machine-shaping, and cheap.By processing modified, the physical and mechanical properties that this resin is outstanding can be given, and replace some engineering plastics thus, having made great progress in general-purpose plastics through engineering approaches in recent years, is the fastest, the most active kind of new varieties of rate of growth in five large general synthetic resins.Although polypropylene and polypropylene alloy material have a wide range of applications at numerous areas, but the molding shrinkage of this type of material is usually between 1.0%-2.0%, much bigger compared to some engineering plastics (as ABS0.4%-0.7%), when processing relatively accurate parts, be limited by very large, only maintenance or while improving original performance, effectively reduce molding shrinkage, polypropylene just likely really replaces engineering plastics.
The current main method improving polypropylene material shrinking percentage is roughly following two kinds: 1, add mineral filler: present method has certain effect, but the toughness of material can be caused to decline; 2, add glass fibre: present method successful, but difficulty of processing improves, and obviously can affect products appearance.
Chinese patent CN102952342A provides a kind of preparation method of Low-shrinkage polypropylene composition, realized by inorganic powder, metallocene linear-low density polyethylene, toughner, weather resisting agent etc., Problems existing is due to inorganic powder large usage quantity, cause composition density to increase considerably, and the goods produced are uncontrollable to polypropylene primary colors on color and luster, be subject to certain restrictions when parts application such as automobiles.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of low-shrinkage polypropylene composite material, while reservation polypropylene advantage performance, effectively reduce its molding shrinkage, widened the Application Areas of polypropylene material; The present invention also provides a kind of its preparation method, rational technology.
Low-shrinkage polypropylene composite material of the present invention, be made up of the raw material of following mass fraction:
Wherein: acrylic resin parallel direction shrinking percentage≤0.7%, vertical direction shrinking percentage≤1.2%, comparatively plain polypropylene shrinking percentage is low for the present invention's acrylic resin used, and this acrylic resin is commercial, is preferably Korea S great Lin polypropylene EC5084.
Described metallocene linear-low density polyethylene adopts prior art preparation, and ethene and high alpha-olefin are produced and obtained under metallocene catalyst effect on gas-phase process device.Wherein high alpha-olefin is preferably the one in 1-butylene, 1-hexene, 1-octene or 1-tetramethyl-amylene, more preferably 1-butylene.
The melt mass flow rate of metallocene linear-low density polyethylene is 0.9-30g/10min, and density is 0.912-0.930g/cm
3, molecular weight distribution is 2-4.The effect adding metallocene linear-low density polyethylene is the molding shrinkage reducing polypropylene composite material, improves the impact property of material simultaneously.
Toughner is the one in EPDM (terpolymer EP rubber), styrene-butadiene rubber(SBR) or POE (polyolefin elastomer), preferred styrene-butadiene rubber(SBR), its effect is the impact property improving material, jointly reduces polypropylene shrinking percentage with metallocene linear-low density polyethylene simultaneously.
Talcum powder particle diameter is 2000-3000 order, talcum powder parts by weight are 0.05-0.5 part, be preferably 0.05-0.3 part, this kind of order number and the talcous of content add, and while can reducing shrinking percentage further, make the matrix material prepared have low-density advantage.In the present invention, each component synergy, reaches the object reducing shrinking percentage to greatest extent, makes matrix material be effectively controlled in raising impact-resistance, reduction density simultaneously.
The preparation method of low-shrinkage polypropylene composite material of the present invention, comprises the following steps:
(1) acrylic resin, metallocene linear-low density polyethylene, toughner and talcum powder are placed in homogenizer, under the rotating speed of 1000 ~ 1500r/min, stir 3-5min, mix;
(2) material mixed is added parallel dual-screw extruding machine melting mixing, extruding pelletization, extrusion temperature is 180 ~ 220 DEG C, forcing machine engine speed 170-190r/min, feeding rotating speed 35-45r/min.
In sum, the present invention has the following advantages:
(1) the present invention adopt low-shrinkage polypropylene based on resin, and add metallocene linear-low density polyethylene, toughner, talcum powder simultaneously, through twin screw extruder extruding pelletization, obtain the modified poly propylene composition with low-shrinkage.
(2) matrix material of the present invention is while reservation polypropylene advantage performance, effectively reduces its molding shrinkage, has widened the Application Areas of polypropylene material.
(3) matrix material of the present invention is widely used in requiring the direct injection moulding production of higher high-grade parts and the base resin for modification once again to shrinking percentage.
(4) the present invention is by adopting different raw materials and proportioning combination, drastically reduce the area the consumption of inorganic powder, while good control composition and shrink of product rate thereof, effectively reduce its density, while further improving performance, under minimizing same volume, the weight of goods provides effective means.
(5) the present invention also provides a kind of its preparation method, rational technology.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1 ~ 4
The each component formula of embodiment 1 ~ 4 is in table 1, and performance index are in table 2.
The each component formula of comparative example 1 ~ 6 is in table 3, and performance index are in table 4.
The preparation process of each embodiment is as follows:
Acrylic resin, metallocene linear-low density polyethylene (mLLDPE), toughner, talcum powder are placed in homogenizer, under the rotating speed of 1400 ± 50r/min, stir 4 ± 1min, mix; Then the Preblend obtained is joined melting mixing in parallel dual-screw extruding machine, extrusion temperature is 200 ± 10 DEG C, forcing machine engine speed 180 ± 10r/min, feeding rotating speed 40 ± 5r/min, extruding pelletization obtains the modified poly propylene composition with low-shrinkage.In embodiment, the melt mass flow rate (MFR) of mLLDPE is 3.7g/10min (test condition: 230 DEG C, counterweight 2.16kg), density 0.913g/cm
3.
By the Low-shrinkage polypropylene composition obtained, adopt the K-TEC85 type injection moulding machine that German MILACRON company produces, prepare test sample.
Test performance is carried out according to respective country standard method of test:
Tensile property is tested according to GB/T1040-2006, adopts 1A type sample, draw speed 50mm/min;
Izod notched impact strength is tested according to GB/T1043-2008;
Bending property is tested according to GB/T9341-2008;
Molding shrinkage presses GB/T17037.4-2003 test, refer to sample shaping after in 16 ~ 24h, size difference between the sample of the drying of measuring at testing laboratory's temperature and its mold cavity of molding, sample is the little square piece of 60 × 60 × 2mm, the length l of test sample
1with width b
1and the length l of mold cavity
0with width b
0, be parallel to the molding shrinkage S in melt flow direction
mp, at the interassay of specimen width; Perpendicular to the molding shrinkage S in melt flow direction
mn, at the interassay of specimen length, calculation formula is: S
mp=100 (l
0-l
1) l
0/ and S
mn=100 (b
0-b
1)/b
0.
Each component proportion (in mass fraction) of table 1 embodiment 1-4
| Each ingredient names | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Acrylic resin | 89.95 | 78.8 | 69.7 | 59.5 |
| mLLDPE | 10 | 18 | 25 | 35 |
| Styrene-butadiene rubber(SBR) | 1 | 3 | 5 | 5 |
| Talcum powder | 0.05 | 0.2 | 0.3 | 0.5 |
The fundamental property data sheet of table 2 embodiment 1-4
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stretching yield stress | MPa | 23.1 | 21 | 19.4 | 19 |
| Flexural strength | MPa | 25.3 | 27.2 | 28.5 | 25.8 |
| Bending elastic modulus | MPa | 930 | 940 | 960 | 954 |
| Izod notched impact strength 23 DEG C | kJ/m2 | 30.1 | 27.1 | 29 | 27.6 |
| Parallel direction shrinking percentage | ％ | 0.63 | 0.55 | 0.55 | 0.55 |
| Vertical direction shrinking percentage | ％ | 0.72 | 0.64 | 0.62 | 0.61 |
| Density | g/cm3 | 0.902 | 0.904 | 0.906 | 0.908 |
Each component proportion (in mass fraction) of table 3 comparative example 1-6
The fundamental property data sheet of table 4 comparative example 1-6
Claims (8)
1. a low-shrinkage polypropylene composite material, is characterized in that: be made up of the raw material of following mass fraction:
2. low-shrinkage polypropylene composite material according to claim 1, is characterized in that: acrylic resin parallel direction shrinking percentage≤0.7%, vertical direction shrinking percentage≤1.2%.
3. low-shrinkage polypropylene composite material according to claim 1, is characterized in that: metallocene linear-low density polyethylene is that ethene and high alpha-olefin are produced and obtained under metallocene catalyst effect on gas-phase process device.
4. low-shrinkage polypropylene composite material according to claim 3, is characterized in that: high alpha-olefin is the one in 1-butylene, 1-hexene, 1-octene or 1-tetramethyl-amylene.
5. low-shrinkage polypropylene composite material according to claim 1, is characterized in that: the melt mass flow rate of metallocene linear-low density polyethylene is 0.9-30g/10min, and density is 0.912-0.930g/cm
3, molecular weight distribution is 2-4.
6. low-shrinkage polypropylene composite material according to claim 1, is characterized in that: toughner is the one in EPDM, styrene-butadiene rubber(SBR) or POE.
7. low-shrinkage polypropylene composite material according to claim 1, is characterized in that: talcum powder particle diameter is 2000-3000 order.
8. a preparation method for the arbitrary described low-shrinkage polypropylene composite material of claim 1-7, is characterized in that: comprise the following steps:
(1) acrylic resin, metallocene linear-low density polyethylene, toughner and talcum powder are placed in homogenizer, under the rotating speed of 1000 ~ 1500r/min, stir 3-5min, mix;
(2) material mixed is added parallel dual-screw extruding machine melting mixing, extruding pelletization, extrusion temperature is 180 ~ 220 DEG C, forcing machine engine speed 170-190r/min, feeding rotating speed 35-45r/min.
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| CN201410251238.1A CN105273301A (en) | 2014-06-06 | 2014-06-06 | Low-shrinkage polypropylene composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974025A (en) * | 2016-10-25 | 2018-05-01 | 合肥杰事杰新材料股份有限公司 | One kind is without filling low-shrink polypropylene composite material and preparation method thereof |
| CN108329641A (en) * | 2017-01-19 | 2018-07-27 | 合肥杰事杰新材料股份有限公司 | A kind of low-crystallinity PP composite material and preparation method thereof |
| CN108329642A (en) * | 2017-01-19 | 2018-07-27 | 合肥杰事杰新材料股份有限公司 | A kind of low-crystallinity polypropene composition and preparation method thereof |
| CN112480552A (en) * | 2020-12-02 | 2021-03-12 | 广东聚石化学股份有限公司 | Polypropylene composite material and preparation method thereof |
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| CN102002186A (en) * | 2010-11-02 | 2011-04-06 | 苏州旭光聚合物有限公司 | Mineral filled low-shrinkage modified polypropylene composite material and preparation method thereof |
| CN102952342A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Low-shrinkage polypropylene composition and preparation method thereof |
| CN102993563A (en) * | 2012-10-26 | 2013-03-27 | 吴玥霖 | Formula of modified polypropylene composite material with low shrinkage rate, and production method thereof |
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2014
- 2014-06-06 CN CN201410251238.1A patent/CN105273301A/en active Pending
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| CN102002186A (en) * | 2010-11-02 | 2011-04-06 | 苏州旭光聚合物有限公司 | Mineral filled low-shrinkage modified polypropylene composite material and preparation method thereof |
| CN102952342A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Low-shrinkage polypropylene composition and preparation method thereof |
| CN102993563A (en) * | 2012-10-26 | 2013-03-27 | 吴玥霖 | Formula of modified polypropylene composite material with low shrinkage rate, and production method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974025A (en) * | 2016-10-25 | 2018-05-01 | 合肥杰事杰新材料股份有限公司 | One kind is without filling low-shrink polypropylene composite material and preparation method thereof |
| CN107974025B (en) * | 2016-10-25 | 2021-08-27 | 合肥杰事杰新材料股份有限公司 | Non-filling low-shrinkage polypropylene composite material and preparation method thereof |
| CN108329641A (en) * | 2017-01-19 | 2018-07-27 | 合肥杰事杰新材料股份有限公司 | A kind of low-crystallinity PP composite material and preparation method thereof |
| CN108329642A (en) * | 2017-01-19 | 2018-07-27 | 合肥杰事杰新材料股份有限公司 | A kind of low-crystallinity polypropene composition and preparation method thereof |
| CN112480552A (en) * | 2020-12-02 | 2021-03-12 | 广东聚石化学股份有限公司 | Polypropylene composite material and preparation method thereof |
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Application publication date: 20160127 |