CN112708196A - Reinforced polypropylene material and preparation method and application thereof - Google Patents
Reinforced polypropylene material and preparation method and application thereof Download PDFInfo
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- CN112708196A CN112708196A CN202011502853.7A CN202011502853A CN112708196A CN 112708196 A CN112708196 A CN 112708196A CN 202011502853 A CN202011502853 A CN 202011502853A CN 112708196 A CN112708196 A CN 112708196A
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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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- 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
- C08K2201/004—Additives being defined by their length
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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
- C08L2205/025—Polymer 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
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a reinforced polypropylene material and a preparation method and application thereof, wherein the preparation method comprises the following steps: 30-70 parts of linear polypropylene; 2-50 parts of long-chain branched polypropylene; 1-20 parts of a compatilizer; 5-60 parts of reinforcing fiber; 0.1-20 parts of fluorine compounds; the polypropylene material prepared by the invention has high surface glossiness, good toughness and high melt strength, and is mainly suitable for blow molding, blister molding and other occasions.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a reinforced 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 reinforced 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 the reinforced polypropylene material which has high surface glossiness, good toughness and high melt strength and 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 reinforced polypropylene material.
The invention is realized by the following technical scheme:
the reinforced polypropylene material comprises the following components in parts by weight:
30-70 parts of linear polypropylene;
2-50 parts of long-chain branched polypropylene;
1-20 parts of a compatilizer;
5-60 parts of reinforcing fiber;
0.1-20 parts of fluorine compounds;
the reinforcing fiber comprises a component I, a component II and a component III, wherein:
a component I: consists of reinforcing fibers with the length of less than 0.1mm, and the number of the reinforcing fibers accounts for 10 to 20 percent, preferably 14 to 18 percent;
and (2) component II: consists of reinforcing fiber with the length of 0.1mm-0.3mm, and the number percentage of the reinforcing fiber is 50-75 percent, preferably 60-70 percent;
and (3) component III: consists of reinforcing fiber with length of 0.4-0.8 mm, and the number percentage of the reinforcing fiber is 5-40%, preferably 15-25%.
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 reinforcing fiber is selected from one or a mixture of several of glass fiber, quartz fiber and basalt fiber; the reinforcing fibers have an average diameter of 5 to 20 microns.
According to the invention, the research shows that the lengths of the reinforced fibers are controlled to be less than 0.1mm, 0.1mm-0.3mm and 0.4mm-0.8mm, and the surface glossiness of the reinforced polypropylene material can be improved and the toughness of the material can be improved by adjusting the distribution content of the lengths, and the melt strength of the material can be improved, so that the reinforced polypropylene material is beneficial to occasions such as blow molding and plastic sucking.
Preferably, the compatilizer is a graft polymer of polar monomer and polypropylene, wherein the polar monomer is one or a mixture of more of maleic anhydride, acrylic acid and acrylate derivatives.
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 reinforced polypropylene material, which comprises the following steps:
weighing the components according to the formula content, uniformly mixing the components except for the reinforced fibers, and adding the mixture into a main feeding system of a double-screw extruder; and simultaneously adding the reinforced fibers into a side feeding system of a double-screw extruder, and then carrying out melt blending, extrusion and granulation by the double-screw extruder to obtain the reinforced polypropylene material.
The twin screw extruder side feed system can be position adjusted and the reinforcing fibers can enter the screw in the first through tenth zones and be added after the extruder die and then directly combined with the polypropylene melt. The reinforced fiber enters the screw through different areas, so that the retention time of the reinforced fiber in the extruder can be adjusted, the shearing degree of the reinforced fiber is controlled, and the retention length of the reinforced fiber is controlled.
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 reinforced 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 reinforced polypropylene material, which comprises linear chain polypropylene, long branched chain polypropylene, a compatilizer, reinforcing fibers and fluorine compounds, wherein the entanglement among molecular chains is increased by utilizing 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.
Compared with the glass fiber material with the conventional length (0.4-0.6 mm), the glass fiber material has high surface glossiness and less floating fibers by controlling the length and the content distribution of the reinforced fibers in the reinforced polypropylene material; the high-toughness high-ductility high-tenacity high-ductility high.
The polypropylene material prepared by the invention has high surface glossiness, good toughness and high 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 1 g/10min (230 ℃, 2.16 Kg load);
linear polypropylene 2: MI was 10 g/10min (230 ℃, 2.16 Kg load);
linear polypropylene 3: MI was 22 g/10min (230 ℃, 2.16 Kg load);
long chain branched polypropylene 1: MI was 2 g/10min (230 ℃, 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 20 g/10min (230 ℃, 2.16 Kg load);
fluorine-based compound 1: polytetrafluoroethylene with the weight-average molecular weight of 40W;
fluorine-based compound 2: polytetrafluoroethylene with the weight-average molecular weight of 600W;
fluorine-based compound 3: polytetrafluoroethylene having a weight average molecular weight of 5W.
A compatilizer:
maleic anhydride grafted polypropylene PP-g-MAH: a manufacturer Polyram; the model is as follows: 1001 CN;
reinforcing fibers:
glass fiber 1: is a glass fiber raw material with the average diameter of 8 microns;
glass fiber 2: the glass fiber is the glass fiber in a modified polypropylene material product, and has the average diameter of 8 microns and the length of 0.4-0.6 mm.
Examples 1 to 11 and comparative examples 1 to 6: preparation of reinforced polypropylene material
Weighing the components according to the formula content, uniformly mixing the components except for the reinforced fibers, and adding the mixture into a main feeding system of a double-screw extruder; and simultaneously adding the reinforced fibers into a side feeding system of a double-screw extruder, and then carrying out melt blending, extrusion and granulation by the double-screw extruder to obtain the reinforced polypropylene material.
Wherein the extruder side-feed system can be adjusted in position and the reinforcing fibers can enter the extruder screw in the first to tenth zones and be added after the extruder die and then directly combined with the polypropylene melt. By adjusting the position of the reinforcing fiber entering the screw of the extruder, the reinforcing fibers with different lengths and content distributions are obtained.
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:
test methods for the length and distribution of the reinforcing fibers: the injection molded sample strip firstly adopts a high-temperature burning scheme to separate the reinforced fiber in the matrix, and then uses an automatic imaging analysis technology to measure the length of the reinforced fiber.
Gloss: ISO 2813-2014; an angle of 60 degrees;
elongation at break: ISO 527-1-2019: and (3) testing conditions are as follows: 23 ℃;
melt strength, melt fracture speed: testing by a melt extensional rheometer, wherein the testing conditions are as follows: 180 ℃;
TABLE 1 concrete compounding ratio (parts by weight) of each component in each example and comparative example and each performance test result
TABLE 1
As can be seen from the above table, the polypropylene material containing the linear polypropylene, the long-chain branched polypropylene, the fluorine compound and the reinforcing fiber 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; comparative example 2 No fluorine-based Compound was added, and its melt
The strength and melt fracture rate are also poor.
As can be seen from the above table of examples 1-2 and comparative examples 3-5, the length and content distribution of the reinforcing fibers affect the gloss and toughness of the material, and also affect the extensibility of the melt of the material.
As can be seen from comparison between examples 1-2 and comparative example 6, the surface glossiness of the glass fiber reinforced polypropylene material is higher than that of the glass fiber material with the conventional length (0.4-0.6 mm) by controlling the length and the content distribution of the reinforced fibers in the reinforced polypropylene material; the elongation at break is large, the toughness is good, and the melt extensibility is good.
Claims (10)
1. The reinforced polypropylene material is characterized by comprising the following components in parts by weight:
30-70 parts of linear polypropylene;
2-50 parts of long-chain branched polypropylene;
1-20 parts of a compatilizer;
5-60 parts of reinforcing fiber;
0.1-20 parts of fluorine compounds;
the reinforcing fiber comprises a component I, a component II and a component III, wherein:
a component I: consists of reinforcing fibers with the length of less than 0.1mm, and the number of the reinforcing fibers accounts for 10 to 20 percent, preferably 14 to 18 percent;
and (2) component II: consists of reinforcing fiber with the length of 0.1mm-0.3mm, and the number percentage of the reinforcing fiber is 50-75 percent, preferably 60-70 percent;
and (3) component III: consists of reinforcing fiber with length of 0.4-0.8 mm, and the number percentage of the reinforcing fiber is 5-40%, preferably 15-25%.
2. The reinforced polypropylene material according to claim 1, wherein the linear polypropylene has a melt index MI of 0.01 to 10 g/10min, at 230 ℃ under a load of 2.16 Kg; preferably 0.1 to 3 g/10 min.
3. The reinforced polypropylene material according to claim 1, wherein the melt index MI of the long chain branched polypropylene is 0.01 to 10 g/10min, the test conditions are 230 ℃ and 2.16 Kg load; preferably 0.1 to 3 g/10 min.
4. The reinforced polypropylene material according to claim 1, wherein the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers and basalt fibers; the reinforcing fibers have an average diameter of 5 to 20 microns.
5. The reinforced polypropylene material of claim 1, wherein the compatibilizer is a graft polymer of a polar monomer and polypropylene, wherein the polar monomer is one or more selected from maleic anhydride, acrylic acid, and acrylate derivatives.
6. The reinforced polypropylene material of claim 1, wherein the fluorine-containing compound is one or more selected from the group consisting of ETFE, PTFE, FEP, PFA, PCTFE, ECTFE, and PVDF.
7. The reinforced polypropylene material according to claim 6, wherein the weight average molecular weight of the fluorine-based compound is 10-1000 ten thousand, preferably 500-800 ten thousand.
8. A process for the preparation of a reinforced polypropylene material according to any one of claims 1 to 7, comprising the steps of:
weighing the components according to the formula content, uniformly mixing the components except for the reinforced fibers, and adding the mixture into a main feeding system of a double-screw extruder; and simultaneously adding the reinforced fibers into a side feeding system of a double-screw extruder, and then carrying out melt blending, extrusion and granulation by the double-screw extruder to obtain the reinforced polypropylene material.
9. The method for preparing the reinforced polypropylene material according to claim 8, wherein the temperature of the first to second zones of the twin-screw extruder is 120 ℃ to 160 ℃, the temperature of the third to fifth zones is 180 ℃ to 300 ℃, the temperature of the fifth to tenth zones is 180 ℃ to 300 ℃, and the screw rotation speed is 300 rpm to 600 rpm.
10. Use of the reinforced polypropylene material according to any one of claims 1 to 7 in blow moulding or blister applications.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011502853.7A CN112708196B (en) | 2020-12-18 | 2020-12-18 | Reinforced polypropylene material and preparation method and application thereof |
| PCT/CN2021/138776 WO2022127859A1 (en) | 2020-12-18 | 2021-12-16 | Reinforced polypropylene material, and preparation method therefor and application thereof |
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| CN202011502853.7A CN112708196B (en) | 2020-12-18 | 2020-12-18 | Reinforced polypropylene material and preparation method and application thereof |
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| CN112708196B CN112708196B (en) | 2022-08-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372651A (en) * | 2021-07-16 | 2021-09-10 | 北海市传创环保科技有限公司 | High-strength and high-toughness polypropylene injection molding material |
| WO2022127859A1 (en) * | 2020-12-18 | 2022-06-23 | 金发科技股份有限公司 | Reinforced polypropylene material, and preparation method therefor and application thereof |
| CN116041849A (en) * | 2022-12-29 | 2023-05-02 | 上海宏盎新材料科技有限公司 | High-strength automobile skylight reinforced polypropylene material and preparation method thereof |
Citations (2)
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|---|---|---|---|---|
| US20170218189A1 (en) * | 2014-10-01 | 2017-08-03 | Japan Polypropylene Corporation | Fiber-reinforced flame-retardant polypropylene resin composition and molded article using the same |
| CN111534037A (en) * | 2020-04-20 | 2020-08-14 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method thereof |
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| CN101074276B (en) * | 2006-05-18 | 2011-06-22 | 中国石油天然气股份有限公司 | Long-chain branching polypropylene and its production |
| JP5255541B2 (en) * | 2009-09-09 | 2013-08-07 | ダイセルポリマー株式会社 | Propylene resin composition |
| CN102558675A (en) * | 2011-12-21 | 2012-07-11 | 上海普利特复合材料股份有限公司 | Polypropylene material with high melt strength and preparation method thereof |
| CN111500009A (en) * | 2020-04-13 | 2020-08-07 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method thereof |
| CN112724510B (en) * | 2020-12-18 | 2022-08-09 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method and application thereof |
| CN112708196B (en) * | 2020-12-18 | 2022-08-09 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method and application thereof |
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- 2020-12-18 CN CN202011502853.7A patent/CN112708196B/en active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170218189A1 (en) * | 2014-10-01 | 2017-08-03 | Japan Polypropylene Corporation | Fiber-reinforced flame-retardant polypropylene resin composition and molded article using the same |
| CN111534037A (en) * | 2020-04-20 | 2020-08-14 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022127859A1 (en) * | 2020-12-18 | 2022-06-23 | 金发科技股份有限公司 | Reinforced polypropylene material, and preparation method therefor and application thereof |
| CN113372651A (en) * | 2021-07-16 | 2021-09-10 | 北海市传创环保科技有限公司 | High-strength and high-toughness polypropylene injection molding material |
| CN116041849A (en) * | 2022-12-29 | 2023-05-02 | 上海宏盎新材料科技有限公司 | High-strength automobile skylight reinforced polypropylene material and preparation method thereof |
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| Publication number | Publication date |
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| CN112708196B (en) | 2022-08-09 |
| WO2022127859A1 (en) | 2022-06-23 |
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