CN111303531A - Low-density polypropylene composite material and preparation method and application thereof - Google Patents
Low-density polypropylene composite material and preparation method and application thereof Download PDFInfo
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- CN111303531A CN111303531A CN201911301956.4A CN201911301956A CN111303531A CN 111303531 A CN111303531 A CN 111303531A CN 201911301956 A CN201911301956 A CN 201911301956A CN 111303531 A CN111303531 A CN 111303531A
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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
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
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Abstract
The invention relates to a low-density polypropylene composite material, which comprises the following raw materials in percentage by weight: 62-90% of polypropylene resin; 2-20% of a toughening agent; 2-11% of talcum powder K; 1-7.5% of talcum powder T; 0.3 to 3 percent of auxiliary agent; the median particle size D50 of the talcum powder K is 4.5-6.5 microns, and the length-diameter ratio is 1-2; the median particle size D50 of the talcum powder T is 1.0-3.0 μm, and the length-diameter ratio is 3.1-4.8. The low-density polypropylene composite material can meet the requirement of light weight of automobiles, can be used for preparing thinner automobile parts, and has strong rigidity, good toughness and good appearance.
Description
Technical Field
The invention relates to the field of polymer materials, in particular to a low-density polypropylene composite material and a preparation method and application thereof.
Background
In recent years, with the rapid development of economy in China, the dependence on petroleum import is increased, the pressure on energy and environmental protection is continuously increased, and the light weight of automobiles becomes the trend of automobile development in the world under the environment that energy conservation and emission reduction are previously emphasized. Experiments prove that if the weight of the whole automobile is reduced by 10%, the fuel efficiency can be improved by 6-8%; the oil consumption can be reduced by 0.3-0.6 liter per hundred kilometers when the mass of the vehicle is reduced by 100 kilograms; the weight of the automobile is reduced by 1 percent, and the oil consumption can be reduced by 0.7 percent.
The approach of automobile light weight mainly has two aspects, firstly, the thickness of the plastic parts is reduced, and secondly, the density of the plastic is reduced. At present, the industry mainly adopts one or two of the methods. The reduction of the thickness of plastic parts and the reduction of the density of plastics are both required on the premise of ensuring that the structural strength of the whole vehicle meets the safety, so that the plastic material is required to meet the requirements of high rigidity, high toughness and high fluidity. The existing plastic modification industry mainly adopts fillers such as talcum powder, mica or crystal whisker to fill so as to improve the rigidity of the material, but the talcum powder with small particle size can improve the rigidity, but the effect is not very obvious; the mica has good filling effect but is difficult to toughen; besides the difficulty in toughening whiskers, the cost is also high. CN102276922A discloses a polypropylene composition with a low linear expansion coefficient and a preparation method thereof, wherein an inorganic filler with a high length-diameter ratio (not less than 5:1) is used to enable the polypropylene composition to have a very low linear expansion coefficient and dimensional stability, but the larger the length-diameter ratio of talcum powder is, the weaker the talcum powder is in the width direction, so that the talcum powder sheet layer is easier to break when impacted, therefore, the larger the length-diameter ratio is, and although the improvement on the rigidity of the material is remarkable, the toughening effect of the material is poor. Moreover, the low-density material adopted by the light weight of the automobile needs high rigidity and high toughness, and a large proportion of toughening agent is added into the material, so that the formed product has obvious tiger skin lines and poor appearance.
Disclosure of Invention
Based on this, the present invention provides a density as low as 0.92 to 1.00g/cm3The polypropylene composite material can meet the requirement of light weight of automobiles, is applied to preparing thinner automobile parts, and can have better product appearance while keeping higher rigidity and toughness.
The specific technical scheme is as follows:
a low-density polypropylene composite material comprises the following raw materials in percentage by weight:
the median particle size D50 of the talcum powder K is 4.5-6.5 microns, and the length-diameter ratio is 1-2;
the median particle size D50 of the talcum powder T is 1.0-3.0 μm, and the length-diameter ratio is 3.1-4.8.
In one embodiment, the weight ratio of talc K to talc T is 1: (0.4-1).
In one embodiment, the weight ratio of talc K to talc T is 1: (0.6-1).
In one embodiment, the talc powder T has a bulk density of 0.9g/cm3～1.0g/cm3。
In one embodiment, the polypropylene resin is at least one selected from homo-polypropylene and co-polypropylene having a melt index of 20 to 95g/10 min.
In one embodiment, the polypropylene resin is formed by mixing PP648U and PP 548R.
In one embodiment, the toughening agent is selected from at least one of ethylene-octene copolymers, polyethylene, hydrogenated styrene-butadiene-styrene block copolymers, and ethylene-propylene-diene monomer rubber.
In one embodiment, the auxiliary agent is selected from at least one of an antioxidant and a weather resistant agent;
in one embodiment, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, and antioxidant DLTP;
the weather resisting agent is at least one selected from hindered amine light stabilizer LA-402AF and UV-3808PP 5.
In one embodiment, the low-density polypropylene composite material comprises the following raw materials in percentage by weight:
the invention also provides a preparation method of the low-density polypropylene composite material.
The specific technical scheme is as follows:
a preparation method of a low-density polypropylene composite material comprises the following steps:
mixing and stirring the polypropylene resin and the toughening agent to obtain a mixture 1;
adding talcum powder K and an auxiliary agent into the mixture 1, and stirring to obtain a mixture 2;
and adding the mixture 2 into an extruder through a main feeding port, adding the talcum powder T into the extruder through a side feeding port, and performing melt extrusion granulation to obtain the talcum powder.
The invention also provides application of the low-density polypropylene composite material in light automobile parts.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, talcum powder with different particle sizes and length-diameter ratios is used as a filling material, and the density of the prepared polypropylene composite material is as low as 0.92-1.00 g/cm3. The talcum powder T with the median particle size D50 of 1.0-3.0 mu m and the length-diameter ratio of 3.1-4.8 has thinner lamella thickness, more number and wide coverage range compared with the common talcum powder with the same weight, and can form a plurality of rigid layers when being filled into a polypropylene material; the talcum powder K with the median particle size D50 of 4.5-6.5 microns and the length-diameter ratio of 1-2 is distributed in a rigid layer formed by the talcum powder T, and when the material is impacted, the talcum powder K with the larger particle size can more effectively hinder the development of cracks, so that the toughness of the material is maintained. Meanwhile, the rigid layer with different length-diameter ratios can properly block the melt surge caused by larger die release expansion, so that the tiger skin texture defect of the product is obviously improved.
The proportional relation between the talcum powder K and the talcum powder T has larger influence on the performances of rigidity and toughness of the polypropylene material. Preferably, the weight ratio of the talcum powder K to the talcum powder T is 1: (0.6-1), and at the moment, the polypropylene material has higher toughness and rigidity and the product appearance is the best.
In the process of preparing the polypropylene composite material, talcum powder T with the median particle size D50 of 1.0-3.0 mu m and the length-diameter ratio of 3.1-4.8 enters an extruder in a side feeding mode to be extruded and granulated, so that the length-diameter ratio of the talcum powder is favorably kept, and the rigidity of the material is improved.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The low density polypropylene composite material of the present invention, its preparation method and use are further described in detail with reference to the following specific examples.
The raw materials used in the following examples are commercially available unless otherwise specified.
Polypropylene resins 648U and 548R, which are co-polypropylene, were purchased from Zhonghai Shell.
Toughener ethylene-octene copolymer, POE DF610, available from mitsui chemistry.
The median particle diameter D50 of talcum powder K is 5 μm, and the length-diameter ratio is 1.5;
talc powder T has a median particle diameter D50 of 2 μm and an aspect ratio of 4.
The talc powder 3 had a median particle diameter D50 of 1.5 μm and an aspect ratio of 15.
The talc powder 4 had a median particle diameter D50 of 1 μm and an aspect ratio of 2.5
The particle size D50 of the wollastonite was 1 μm, and the aspect ratio was 6.
The auxiliary agent is antioxidant and weather resisting agent selected from BASF antioxidant Irganox 1010, BASF antioxidant Irgafos168 and ADEKA weather resisting agent LA-402 AF.
Preparation method
The preparation method of the polypropylene composite material comprises the following steps:
adding the polypropylene resin and the toughening agent ethylene-octene copolymer POE DF610 into a stirrer, and stirring for 4min at the rotating speed of 280r/min to obtain a mixture 1.
Adding talcum powder K, antioxidant Irganox 1010, antioxidant Irgafos168 and weather resisting agent LA-402AF into the mixture 1, and stirring for 6min at the rotating speed of higher than 400r/min to obtain a mixture 2.
And adding the mixture 2 into a double-screw extruder through a main feeding port for extrusion granulation, adding talcum powder T or talcum powder 3 or talcum powder 4 or wollastonite into the extruder together in a side feeding mode, and performing melt extrusion granulation to obtain the polypropylene composite material. The rotating speed frequency of the double-screw extruder is 40Hz, the temperature zone I is 160 ℃, the rest temperature is 180-240 ℃, and the vacuum degree is more than minus 0.06 MPa.
Performance testing
The performance test method of the polypropylene composite material comprises the following steps:
(1) tensile strength was tested according to ISO 527:2012 standard;
(2) the flexural strength and flexural modulus were tested according to the ISO 178:2010 standard;
(3) the notched impact strength is tested according to the ISO 180:2000 standard;
(4) MFR was measured according to ISO 1133:2011 at 230 ℃ under 2.16 kg;
(5) density was tested according to ISO 1183:2012 standard;
(6) the appearance grade was formed into a standard sample according to the YR method, and the tiger stripe grade was visually evaluated.
Examples 1 to 6 and results of Performance test
Polypropylene composites were prepared according to the formulation described in table 1 and the composites were tested for performance, the results are shown in table 1.
TABLE 1
Wherein the bulk density of the talcum powder T is 1.0g/cm3。
Example 4 and comparative examples 1-5 and performance test results
Polypropylene composites were prepared according to the formulation described in Table 2 and the composites were tested for properties using the same test methods as examples 1-8, with the results shown in Table 2.
TABLE 2
As can be seen from tables 1 and 2, the polypropylene composites obtained in examples 1 to 8 all had lower density and better rigidity, and maintained better toughness and good appearance. In examples 3 to 8, the total filling amount of talc powder K and talc powder T was constant, the ratio of talc powder K to talc powder T was changed, and the properties of the polypropylene composite material were also changed in various aspects, and the polypropylene composite material prepared according to the formulation ratio of example 4 had the best overall properties and appearance, i.e., the density was lower than 1.00g/cm3, the highest rigidity (flexural modulus reached 2123MPa), and still maintained high toughness (notched impact strength 33.0kJ/m2), and the appearance rating was the best 10. When the polypropylene composite materials of examples 3 to 8 were analyzed for their properties, the weight ratio of the two materials was 1: (0.6-1), the polypropylene composite material has excellent comprehensive performance, the appearance is over 8 grades, the rigidity of the material is obviously improved along with the increase of the content of the talcum powder T, the toughness is slightly reduced, and the appearance grade of the product is obviously improved.
Compared with the embodiment 4, the formula of the comparative example 1 and the formula of the comparative example 3 are only respectively added with the talcum powder K and the talcum powder T, and the prepared polypropylene material cannot have good rigidity and toughness at the same time, and has poor comprehensive performance and appearance; comparative example 4 talc powder K and talc powder 4(D50 is 1 μm, aspect ratio is 2.5) were used in combination, and it can be seen that the aspect ratio of talc powder 4 is less than 3.1, the toughness of the polypropylene material is higher, but the rigidity is lower, the appearance is poorer, and the comprehensive properties are not as good as those of example 4; comparative example 5 talc K was used in combination with talc 3(D50 1.5 μm, aspect ratio 15) and it can be seen that talc 3 has an aspect ratio of > 4.8 and the polypropylene material is more rigid but less tough and has less overall properties and appearance than example 4. In comparative example 2, wollastonite was used instead of talc to produce a polypropylene material having greater stiffness but poorer toughness and appearance.
As can be seen from the above examples 1-8 and comparative examples 1-5, the aspect ratio selection and weight ratio between talc K and talc T have a significant effect on the stiffness, toughness and appearance of the low density polypropylene.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The low-density polypropylene composite material is characterized by comprising the following raw materials in percentage by weight:
the median particle size D50 of the talcum powder K is 4.5-6.5 microns, and the length-diameter ratio is 1-2;
the median particle size D50 of the talcum powder T is 1.0-3.0 μm, and the length-diameter ratio is 3.1-4.8.
2. The low density polypropylene composite of claim 1, wherein the weight ratio of talc powder K to talc powder T is 1: (0.4 to 1).
3. The low density polypropylene composite of claim 2, wherein the weight ratio of talc K to talc T is 1: (0.6-1).
4. The low density polypropylene composite of claim 1, wherein the talc T has a bulk density of 0.9g/cm3～1.0g/cm3。
5. The low density polypropylene composite according to any one of claims 1 to 4, wherein the polypropylene resin is at least one selected from homo-polypropylene and co-polypropylene having a melt index of 20 to 95g/10 min.
6. The low density polypropylene composite of claim 5, wherein the polypropylene resin is a blend of PP648U and PP 548R.
7. The low density polypropylene composite of any one of claims 1 to 4, wherein the toughening agent is selected from at least one of ethylene-octene copolymer, polyethylene, hydrogenated styrene-butadiene-styrene block copolymer, and ethylene propylene diene monomer;
the auxiliary agent is selected from at least one of an antioxidant and a weather resisting agent;
8. the low density polypropylene composite according to any one of claims 1 to 4, comprising the following raw materials in weight percent:
9. a method for preparing a low density polypropylene composite according to any one of claims 1 to 8, comprising the steps of:
mixing and stirring the polypropylene resin and the toughening agent to obtain a mixture 1;
adding talcum powder K and an auxiliary agent into the mixture 1, and stirring to obtain a mixture 2;
and adding the mixture 2 into an extruder through a main feeding port, adding the talcum powder T into the extruder through a side feeding port, and performing melt extrusion granulation to obtain the talcum powder.
10. Use of the low density polypropylene composite of any one of claims 1 to 8 in light weight automotive parts.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679862A (en) * | 2020-12-14 | 2021-04-20 | 金发科技股份有限公司 | Polypropylene composition 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 |
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| CN107043489A (en) * | 2016-12-27 | 2017-08-15 | 天津金发新材料有限公司 | A kind of low-density height flowing high rigidity talc powder filled polypropylene material |
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| CN109651710A (en) * | 2018-12-26 | 2019-04-19 | 天津金发新材料有限公司 | High-fluidity high-toughness low-density talc powder filled polypropylene material and preparation method thereof |
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| US5219913A (en) * | 1990-09-12 | 1993-06-15 | Idemitsu Petrochemical Company, Ltd. | Polypropylene-based resin composition |
| JPH0987422A (en) * | 1995-09-22 | 1997-03-31 | Nippon G Ii Plast Kk | Resin composition |
| CN104059286A (en) * | 2013-03-22 | 2014-09-24 | 上海金发科技发展有限公司 | Polypropylene compound for automobile fender and preparation method thereof |
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| CN108219342A (en) * | 2018-01-18 | 2018-06-29 | 金发科技股份有限公司 | A kind of polypropylene composite material for automobile bumper and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679862A (en) * | 2020-12-14 | 2021-04-20 | 金发科技股份有限公司 | Polypropylene composition 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 |
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