CN112724508A - High-melt-strength polypropylene material and preparation method and application thereof - Google Patents

High-melt-strength polypropylene material and preparation method and application thereof Download PDF

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Publication number
CN112724508A
CN112724508A CN202011502849.0A CN202011502849A CN112724508A CN 112724508 A CN112724508 A CN 112724508A CN 202011502849 A CN202011502849 A CN 202011502849A CN 112724508 A CN112724508 A CN 112724508A
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melt strength
polypropylene
parts
polypropylene material
high melt
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CN202011502849.0A
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Chinese (zh)
Inventor
陆湛泉
黄险波
叶南飚
陈平绪
程文建
程书文
姜向新
杨霄云
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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Priority to CN202011502849.0A priority Critical patent/CN112724508A/en
Publication of CN112724508A publication Critical patent/CN112724508A/en
Priority to PCT/CN2021/138775 priority patent/WO2022127858A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/04Polymer mixtures characterised by other features containing interpenetrating networks

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high melt strength polypropylene material and a preparation method and application thereof, wherein the preparation method comprises the following steps: 10-90 parts of linear polypropylene; 0.5-50 parts of long-chain branched polypropylene; 0.01-20 parts of fluorine compounds. The invention utilizes the long molecular chain of the linear chain polypropylene to increase the entanglement among the molecular chains, which is beneficial to improving the stability of the melt during extrusion and plastic suction; the addition of the long-chain branch polypropylene can greatly improve the melt strength by utilizing the branch chain structure; the fluorine compound is not melted in the forming process and can be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers can form an interpenetrating network, and the melt strength of the whole material is further improved. The polypropylene material prepared by the invention has higher melt strength and is mainly suitable for blow molding, blister molding and other occasions.

Description

High-melt-strength polypropylene material and preparation method and application thereof
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a high-melt-strength polypropylene material and a preparation method and application thereof.
Background
The polypropylene material is a polymer material with the largest consumption at present, has the advantages of excellent processability, mechanical property and the like, and is widely applied to the fields of daily life and industrial production, such as: agricultural films, wire and cable, communications, building construction, aerospace manufacturing, and the like.
Polyolefin materials currently available for blow molding and blister molding are essentially pure HDPE or PP resins, which are well formable but require improvement in heat resistance and strength. The high strength and high rigidity of glass fiber are generally utilized in the industry to improve the strength and heat resistance of products, but the conventional glass fiber reinforced polypropylene material has the problems of low melt strength, low melt elongation, floating fiber on the surface, poor toughness and the like.
Therefore, there is a need to develop a high melt strength polypropylene material suitable for blow molding and blister molding.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a polypropylene material with high melt strength, which is beneficial to occasions such as blow molding, plastic sucking and the like.
Another object of the present invention is to provide a method for preparing the above high melt strength polypropylene material.
The invention is realized by the following technical scheme:
the high melt strength polypropylene material comprises the following components in parts by weight:
10-90 parts of linear polypropylene;
0.5-50 parts of long-chain branched polypropylene;
0.01-20 parts of fluorine compounds.
As a further preferred embodiment of the present invention, the high melt strength polypropylene material comprises the following components in parts by weight:
40-75 parts of linear polypropylene;
20-40 parts of long-chain branched polypropylene;
8-20 parts of fluorine compounds.
Preferably, the linear polypropylene has a melt index MI of 0.01-10 g/10min, a test condition of 230 ℃ and a load of 2.16 Kg; preferably 0.1 to 3 g/10 min.
Preferably, the melt index MI of the long-chain branched polypropylene is 0.01-10 g/10min, the test condition is 230 ℃ and the load is 2.16 Kg; preferably 0.1 to 3 g/10 min.
Preferably, the fluorine compound is one or a mixture of several of ethylene-tetrafluoroethylene copolymer (ETFE), Polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy resin (PFA), Polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), or polyvinylidene fluoride (PVDF).
The invention prefers the fluorine compound with high molecular weight, which is not melted in the forming process and can be drawn into fiber under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fiber can form an interpenetrating network, thereby further improving the melt strength of the whole material. The molecular weight is too low to improve the melt strength, and the molecular weight is too high to affect the processability, so that the weight average molecular weight of the fluorine-based compound is preferably 10 to 1000 ten thousand, and preferably 500-800 ten thousand.
The invention also provides a preparation method of the high melt strength polypropylene material, which comprises the following steps: weighing the components according to the formula content, uniformly mixing the components, and adding the mixture into a main feeding system of a double-screw extruder; then the high melt strength polypropylene material is prepared by melt blending and extrusion granulation through a double-screw extruder.
Preferably, the temperature of the first zone to the second zone of the double-screw extruder is 120-160 ℃, the temperature of the third zone to the fifth zone is 180-300 ℃, the temperature of the fifth zone to the tenth zone is 180-300 ℃, and the rotating speed of the screw is 300-600 rpm.
The invention also provides the application of the high melt strength polypropylene material in blow molding and plastic uptake occasions.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a high melt strength polypropylene material, which comprises linear chain polypropylene, long branched chain polypropylene and fluorine compounds, wherein the entanglement among molecular chains is increased by using the long molecular chains of the linear chain polypropylene, so that the stability of a melt during extrusion and plastic suction is improved; the addition of the long-chain branch polypropylene can greatly improve the melt strength by utilizing the branch chain structure; the high molecular weight fluorine compound is not melted in the forming process and can be stretched into fiber under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fiber can form an interpenetrating network, and the melt strength of the whole material is further improved.
The polypropylene material prepared by the invention has higher melt strength and is mainly suitable for blow molding, blister molding and other occasions.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials adopted in the examples and the comparative examples of the invention are all from commercial sources;
linear polypropylene 1: MI was 2 g/10min (230 ℃, 2.16 Kg load);
linear polypropylene 2: MI was 8 g/10min (230 ℃, 2.16 Kg load);
linear polypropylene 3: MI was 20 g/10min (230 ℃, 2.16 Kg load);
long chain branched polypropylene 1: MI was 3 g/10min (230 ℃ C., 2.16 Kg load);
long chain branched polypropylene 2: MI was 10 g/10min (230 ℃, 2.16 Kg load);
long chain branched polypropylene 3: MI was 25 g/10min (230 ℃, 2.16 Kg load);
fluorine-based compound 1: polytetrafluoroethylene with weight-average molecular weight of 50W;
fluorine-based compound 2: polytetrafluoroethylene with the weight-average molecular weight of 500W;
fluorine-based compound 3: polytetrafluoroethylene having a weight average molecular weight of 1W.
Examples 1 to 11 and comparative examples 1 to 2: preparation of high melt strength polypropylene material
Weighing the components according to the formula content in the table 1, uniformly mixing the components, and adding the mixture into a main feeding system of a double-screw extruder; then the polypropylene material is prepared by melt blending and extrusion granulation through a double-screw extruder.
Wherein the temperature of the first zone to the second zone of the extruder is 120-160 ℃, the temperature of the third zone to the fifth zone is 180-300 ℃, the temperature of the fifth zone to the tenth zone is 180-300 ℃, and the rotating speed of the screw is 300-600 rpm.
Test criteria or methods for each property:
melt strength: testing by a melt extensional rheometer, wherein the testing conditions are as follows: 180 ℃;
melt fracture speed: testing by a melt extensional rheometer, wherein the testing conditions are as follows: 180 ℃ is carried out.
TABLE 1 concrete compounding ratio (parts by weight) of each component in each example and comparative example and each performance test result
Figure 681066DEST_PATH_IMAGE002
As can be seen from the above table, the polypropylene material containing linear polypropylene, long-chain branched polypropylene and fluorine compounds of the invention has obviously improved melt strength and melt fracture speed, and is suitable for blow molding, blister molding and other occasions. Comparative example 1, in which no long-chain branched polypropylene was added, the melt strength and the melt fracture rate were poor; in comparative example 2, the long-chain branched polypropylene is introduced, but the fluorine compound is not added, so that the melt strength and the melt fracture speed are slightly improved, but the improvement effect is not obvious, and the synergistic effect among the components can be shown.

Claims (9)

1. The high melt strength polypropylene material is characterized by comprising the following components in parts by weight:
10-90 parts of linear polypropylene;
0.5-50 parts of long-chain branched polypropylene;
0.01-20 parts of fluorine compounds.
2. The high melt strength polypropylene material of claim 1, comprising the following components in parts by weight:
40-75 parts of linear polypropylene;
20-40 parts of long-chain branched polypropylene;
8-20 parts of fluorine compounds.
3. The high melt strength polypropylene material according to claim 1 or 2, wherein the linear polypropylene has a melt index MI of 0.01 to 10 g/10min, test conditions of 230 ℃, 2.16 Kg load; preferably 0.1 to 3 g/10 min.
4. The high melt strength polypropylene material according to claim 1 or 2, wherein the melt index MI of the long chain branched polypropylene is 0.01-10 g/10min, the test conditions are 230 ℃ and 2.16 Kg load; preferably 0.1 to 3 g/10 min.
5. The high melt strength polypropylene material according to claim 1 or 2, wherein the fluorine compound is one or more selected from the group consisting of ETFE, PTFE, FEP, PFA, PCTFE, ECTFE, and PVDF.
6. The high melt strength polypropylene material according to claim 5, wherein the weight average molecular weight of the fluorine-based compound is 10-1000 ten thousand, preferably 500-800 ten thousand.
7. The process for preparing a high melt strength polypropylene material according to any one of claims 1 to 6, comprising the steps of:
weighing the components according to the formula content, uniformly mixing the components, and adding the mixture into a main feeding system of a double-screw extruder; then the high melt strength polypropylene material is prepared by melt blending and extrusion granulation through a double-screw extruder.
8. The method for preparing a high melt strength polypropylene material according to claim 7, wherein the temperature of the first to second zones of the twin-screw extruder is 120-160 ℃, the temperature of the third to fifth zones is 180-300 ℃, the temperature of the fifth to tenth zones is 180-300 ℃, and the screw rotation speed is 300-600 rpm.
9. Use of a high melt strength polypropylene material according to any one of claims 1 to 6 in blow moulding or blister applications.
CN202011502849.0A 2020-12-18 2020-12-18 High-melt-strength polypropylene material and preparation method and application thereof Pending CN112724508A (en)

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PCT/CN2021/138775 WO2022127858A1 (en) 2020-12-18 2021-12-16 High-melt-strength polypropylene material, preparation method therefor and use thereof

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WO2022127858A1 (en) * 2020-12-18 2022-06-23 金发科技股份有限公司 High-melt-strength polypropylene material, preparation method therefor and use thereof
CN115216092A (en) * 2022-07-29 2022-10-21 横店集团得邦工程塑料有限公司 Low-temperature-resistant reinforced halogen-free flame-retardant PP/HMSPP composite material and preparation method thereof
CN117946490A (en) * 2024-03-26 2024-04-30 哈尔滨理工大学 Polypropylene composite material with excellent high temperature resistance and irradiation resistance and preparation method thereof

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CN116790083B (en) * 2023-04-28 2024-07-26 江苏上上电缆集团新材料有限公司 Low-dielectric-loss modified polypropylene insulation cable material and preparation method thereof

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CN115216092A (en) * 2022-07-29 2022-10-21 横店集团得邦工程塑料有限公司 Low-temperature-resistant reinforced halogen-free flame-retardant PP/HMSPP composite material and preparation method thereof
CN115216092B (en) * 2022-07-29 2024-04-30 横店集团得邦工程塑料有限公司 Low-temperature-resistant reinforced halogen-free flame-retardant PP/HMSPP composite material and preparation method thereof
CN117946490A (en) * 2024-03-26 2024-04-30 哈尔滨理工大学 Polypropylene composite material with excellent high temperature resistance and irradiation resistance and preparation method thereof

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