CN112679842B - Polypropylene composition capable of efficiently improving flow marks and preparation method and application thereof - Google Patents
Polypropylene composition capable of efficiently improving flow marks and preparation method and application thereof Download PDFInfo
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- CN112679842B CN112679842B CN202011469994.3A CN202011469994A CN112679842B CN 112679842 B CN112679842 B CN 112679842B CN 202011469994 A CN202011469994 A CN 202011469994A CN 112679842 B CN112679842 B CN 112679842B
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Abstract
The invention discloses a polypropylene composition for efficiently improving flow marks, which comprises a flow mark improving agent, wherein the flow mark improving agent is high-molecular-weight homopolymerized polypropylene and has a melt flow rate under the test conditions of 230 ℃ and 2.16kg<0.5g/10min, weight average molecular weight Mw>1.5×106g/mol. When the weight percentage of the flow mark improver in the polypropylene composition is 0.2-4%, the flow mark of the polypropylene composition can be effectively improved. The invention provides a new method for improving the flow marks on the surface of the polypropylene material, fundamentally solves the problem of the flow marks on the surface of the polypropylene material, further improves the mechanical property of the material, does not obviously reduce the melt flow rate of a material system, and avoids the occurrence of other injection molding defects.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polypropylene composition for efficiently improving flow marks, and a preparation method and application thereof.
Background
In the injection molding process of the modified polypropylene, especially when large-size plastic parts such as automobile instrument panels, bumpers, door panels or other plastic parts with long flow and large area are prepared, the surface of the product is easy to have the defect similar to tiger skin lines, which is also called flow marks, and the appearance quality of the product is seriously influenced by the defect.
In the prior art, the flow marks are generally improved by compounding two or more kinds of polypropylene with different melt indexes, wherein the content of the polypropylene with a low melt index is required to be higher, the total dosage is also required to be higher, and the flow marks cannot be efficiently improved. For example, CN106147033B discloses a tiger-stripe-free polypropylene composite material and a preparation method and application thereof, wherein the adopted tiger-stripe remover is composed of three polypropylenes with melt indexes of 80-110 g/10min, 50-70 g/10min and 30-40 g/10min, the polypropylene content of 30-40 g/10min is high, and the addition amount of the tiger-stripe remover in the formula is large.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a polypropylene composition for efficiently improving flow marks, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polypropylene composition for effectively improving flow marks comprises a flow mark improving agent, wherein the flow mark improving agent is high-molecular-weight homopolymerized polypropylene and has a melt flow rate of 2.16kg at 230 DEG C<0.5g/10min, weight average molecular weight Mw>1.5×106g/mol。
The inventor researches and discovers that the root cause of the generation of the flow mark is the unstable flow of the melt and has great relation with the elasticity of the melt, and the polypropylene with high molecular weight is added into the polypropylene composition to improve the elasticity of the melt, so that the problem of the flow mark can be fundamentally solved. Test results show that the elasticity of the melt can be effectively improved by adding a small amount of the high molecular weight homo-polypropylene into the polypropylene material, and the effect of efficiently improving the flow marks on the surface of the material is achieved. Moreover, no matter the material is a pure polypropylene system or a polypropylene composition system, the high molecular weight homo-polypropylene can play a role in efficiently improving the flow marks.
Preferably, in the polypropylene composition for efficiently improving flow marks, the weight percentage of the flow mark improver is 0.2-4%. When the content of the flow mark improver in the polypropylene composition is 0.2-4%, the surface flow mark of the polypropylene composition can be effectively improved, the melt flow rate of a polypropylene composition system can not be obviously reduced, and injection molding defects such as an insufficient injection phenomenon and the like are avoided. If the addition amount of the flow mark improver is too high, the melt flow rate of the system is remarkably reduced; if the amount is too low, the flow mark improving effect is not significant.
Preferably, in the polypropylene composition for efficiently improving flow marks, the weight percentage of the flow mark improving agent is 1-3%. When the flow mark improver is added into the polypropylene composition in the amount, the flow mark improver has a good effect of improving the surface flow marks of the polypropylene composition, and has a small influence on the melt flow rate of a polypropylene composition system.
Preferably, the polypropylene composition for efficiently improving the flow mark further comprises the following components in percentage by weight: 40-98% of polypropylene, 0-12% of polyethylene, 0-30% of toughening agent, 0-40% of filler, 0.1-0.5% of antioxidant and 0.1-1% of processing aid.
Preferably, the polypropylene is at least one of homo-polypropylene and co-polypropylene, and the melt flow rate of the polypropylene is more than or equal to 15g/10min at 230 ℃ under the test condition of 2.16 kg.
Preferably, the polyethylene is high-density polyethylene, and the melt flow rate of the polyethylene is 0.5-30 g/10min under the test conditions of 190 ℃ and 2.16 kg.
Preferably, the melt flow rate of the toughening agent is 0.1-30 g/10min at 190 ℃ under the test condition of 2.16 kg.
Preferably, the toughening agent is at least one of ethylene-alpha olefin copolymer, hydrogenated styrene-butadiene block copolymer and ethylene propylene diene monomer.
Preferably, in the above technical means, the filler is at least one of talc, whisker, calcium carbonate, barium sulfate and wollastonite.
Preferably, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant comprises a hindered phenol antioxidant, and the auxiliary antioxidant comprises a phosphite antioxidant.
In the present invention, the processing aid includes a colorant, a lubricant, and the like.
As another aspect of the above technical solution, the present invention further provides a preparation method of the polypropylene composition for efficiently improving flow marks, which includes the following steps:
(1) weighing the components according to a formula, adding all the components into a high-speed mixer, and mixing for 1-3 min at the rotating speed of 1000-2000 RPM to obtain a premix;
(2) and (3) melting and extruding the premix through a double-screw extruder, wherein the temperature of each zone of a screw is 190-230 ℃, and carrying out vacuum granulation to obtain the polypropylene composition for efficiently improving the flow marks.
As another aspect of the technical scheme, the invention further provides an application of the polypropylene composition for efficiently improving the flow marks in the preparation of automotive upholsteries. The automotive interior part comprises an instrument panel, an auxiliary instrument panel, a stand column, a glove box, a door panel, a threshold, an automobile lamp support and the like.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a new method for improving the surface flow marks of the polypropylene material, namely, the melt elasticity is improved by adding a small amount of the homopolymerized polypropylene with specific high molecular weight into a polypropylene composition system, so that the problem of the surface flow marks of the material is fundamentally solved, and the effect of efficiently improving the surface flow marks of the material is achieved. The invention effectively improves the flow marks on the surface of the material, further improves the mechanical property of the material, does not obviously reduce the melt flow rate of a material system, and avoids the occurrence of other injection molding defects. The polypropylene composition is used for preparing automobile interior parts such as instrument panels, auxiliary instrument panels, stand columns, glove boxes, door plates, doorsills, car lamp supports, air conditioner shells and the like, and the products have good appearance quality.
Detailed Description
The technical solutions of the present invention will be further described with reference to the following embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In the examples, the percentages are by weight unless otherwise specified. The methods in the examples are conventional in the art unless otherwise specified.
The sources of the raw materials used in the examples and comparative examples are as follows:
(1) the flow mark improver-1 is homo-polypropylene and is purchased from: exxonmobil having a melt flow rate of 0.2g/10min under 2.16kg test conditions at 230 ℃ and a weight average molecular weight Mw of 1.62X 106g/mol；
(2) The flow mark improver-2 is homopolymerized polypropylene, and has the following types: PP B1101, manufacturer: yanshan petrochemical having a melt flow rate of 0.7g/10min at 230 ℃ under 2.16kg test conditions and a weight average molecular weight Mw of 5.8X 105g/mol；
(3) Polypropylene, type number: PP H9018 with a melt flow rate of 54g/10min at 230 ℃ under 2.16kg test conditions, available from: landification;
(4) polypropylene, type number: PP K9017 with a melt flow rate of 16.3g/10min at 230 ℃ under 2.16kg test conditions, available from: taiwan taiji (taiwan area);
(5) high density polyethylene, type: HDPE 5000S, having a melt flow rate of 1g/10min at 190 ℃ under 2.16kg test conditions, was obtained from: petrifying the winners;
(6) the toughening agent is an ethylene-alpha olefin copolymer, and the type is as follows: POE DF610 having a melt flow rate of 1.2g/10min at 190 ℃ under 2.16kg test conditions was purchased from: chemical of three wells;
(7) the filler is talcum powder, and the type is as follows: TYT-777A, purchased from: a source of north sea;
(8) the antioxidant consists of a main antioxidant and an auxiliary antioxidant, and the weight ratio of the main antioxidant to the auxiliary antioxidant is 1: 1; wherein, the main antioxidant is hindered phenol antioxidant, and the model is as follows: irganox 1010, available from: basf; the auxiliary antioxidant is phosphite ester antioxidant, and the type is as follows: irganox 168, available from: basf;
(9) processing aid
Black seed (pigment), type: PE2772, from: a cabot;
lubricant, model EBS B50, available from: indonesia.
Performance test standard:
and (3) performing injection molding on the polypropylene composition particles at 190-220 ℃ by using an injection molding machine to obtain the following standard sample strips for testing:
flow mark: a smooth rectangular thin flat plate of 328mm by 108mm by 2mm was injection molded for flow mark evaluation. Visually observing, grading according to the obvious degree of the flow marks, wherein the flow marks are obviously more than slight and not obvious and more than none;
tensile strength: testing was performed according to ISO 527: 1993;
flexural strength and flexural modulus: testing according to ISO 178:2001 standard;
impact strength: testing according to ISO 180:2000 standard;
melt flow rate: the test was carried out according to ISO 1133:2011 standard.
The formulations of the polypropylene compositions of examples 1 to 8 and comparative examples 1 to 5 are shown in tables 1 to 2, and the preparation methods are as follows:
(1) weighing each component according to a formula, adding all the components into a high-speed mixer, and mixing for 1-3 min at the rotating speed of 1000-2000 RPM to obtain a premix;
(2) and melting and extruding the premix by a double-screw extruder, wherein the temperature of each zone of a screw is 190-230 ℃, and carrying out vacuum granulation to obtain the polypropylene composition.
TABLE 1
TABLE 2
Note: in the table, "-" indicates that the component was not added.
And (4) analyzing results:
as can be seen from examples 1 to 8 and comparative example 1, the surface flow mark of the modified PP containing the flow mark improver of the present invention (i.e., flow mark improver-1) can be effectively improved; when the content of the flow mark improver-1 in the composition is 0.2-4%, the flow mark of the product can be effectively improved, and the melt flow rate of the PP composition can not be obviously reduced; particularly, when the content of the flow mark improver-1 in the PP composition is 1-3%, the flow mark improver can not only effectively improve the flow mark of a product, but also has small influence on the melt flow rate of the composition and has better use effect. It can be seen from example 1 that when the content of the flow mark improver is too low, the flow mark improver has no obvious effect on the flow mark improvement effect of the product; it can also be seen from example 8 that too high a content of the flow mark improver according to the present invention results in a significant decrease in the melt flow rate of the PP composition, and is liable to cause injection molding defects such as short shot. It can also be seen from comparative example 2 that the flow mark of the product could not be effectively improved by replacing the flow mark improver of the present invention with another homopolypropylene (e.g., flow mark improver-2), indicating that the melt flow rate was not improved until the addition of the homopolypropylene was carried out at 230 ℃ under the 2.16kg test condition<0.5g/10min, and weight average molecular weight Mw>1.5×106The flow mark of the product can be effectively improved under the condition of less adding amount when the homopolymerized polypropylene is used in g/mol.
From example 9 it can be seen that the flow mark improver of the present invention is still able to improve the flow mark of the product with high efficiency even for the modified PP system with higher filler content and lower toughener content.
From example 10 and comparative example 3 it can be seen that the flow mark improving agent of the present invention is also highly effective in improving the flow mark of the product for a pure polypropylene system (i.e. non-modified PP) without significantly affecting the melt flow rate of the material system. It can also be seen from comparative example 4 that other homopolypropylenes (e.g.flow mark improver-2) are not effective in improving product flow marks in the neat PP system.
The tests also show that the flow mark improver is suitable for polypropylene materials with larger melt flow rate (more than 30g/10min) and also suitable for polypropylene materials with smaller melt flow rate (less than 30g/10min), and has wide application range.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. The polypropylene composition for effectively improving the flow marks is characterized by comprising the following components in percentage by weight: 40-98% of polypropylene, 0-12% of polyethylene, 0-30% of toughening agent, 0-40% of filler, 0.1-0.5% of antioxidant and 0.1-1% of processing aid, wherein the polypropylene is at least one of homo-polypropylene and co-polypropylene, and the melt flow rate of the polypropylene under the test conditions of 230 ℃ and 2.16kg is more than or equal to 15g/10 min; also comprises a flow mark improving agent which is high molecular weight homopolymerized polypropylene with the melt flow rate of 2.16kg at 230 DEG C<0.5g/10min, weight average molecular weight Mw>1.5×106g/mol; in the polypropylene composition for efficiently improving the flow marks, the weight percentage of the flow mark improver is 0.2-4%.
2. The polypropylene composition with high flow mark improving efficiency as claimed in claim 1, wherein the polypropylene composition with high flow mark improving efficiency is characterized in that the weight percentage of the flow mark improving agent is 1% to 3%.
3. The polypropylene composition with high flow mark improving efficiency as claimed in claim 1, wherein the polyethylene is high density polyethylene, and the melt flow rate of the polyethylene is 0.5-30 g/10min under the test condition of 2.16kg at 190 ℃.
4. The polypropylene composition with high flow mark improving efficiency as claimed in claim 1, wherein the melt flow rate of the toughening agent is 0.1-30 g/10min at 190 ℃ under the test condition of 2.16 kg.
5. The polypropylene composition with high flow mark improving efficiency as claimed in claim 1, wherein the toughening agent is at least one of ethylene-alpha olefin copolymer, hydrogenated styrene-butadiene block copolymer and ethylene propylene diene monomer.
6. The preparation method of the polypropylene composition for effectively improving the flow marks as claimed in any one of claims 1 to 5, wherein the method comprises the following steps:
(1) weighing each component according to a formula, adding all the components into a high-speed mixer, and mixing for 1-3 min at the rotating speed of 1000-2000 RPM to obtain a premix;
(2) and (3) carrying out melt extrusion on the premix through a double-screw extruder, wherein the temperature of each zone of a screw is 190-230 ℃, and carrying out vacuum granulation to obtain the polypropylene composition for efficiently improving the flow marks.
7. The use of the polypropylene composition with high efficiency for improving flow marks as defined in any one of claims 1 to 5 in the preparation of automotive interior parts.
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| WO2018107950A1 (en) * | 2016-12-13 | 2018-06-21 | 金发科技股份有限公司 | Method for eliminating tiger stripe defect from polypropylene composition and polypropylene composition prepared by same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018107950A1 (en) * | 2016-12-13 | 2018-06-21 | 金发科技股份有限公司 | Method for eliminating tiger stripe defect from polypropylene composition and polypropylene composition prepared by same |
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