CN108752743B - Long glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Long glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN108752743B CN108752743B CN201810579967.8A CN201810579967A CN108752743B CN 108752743 B CN108752743 B CN 108752743B CN 201810579967 A CN201810579967 A CN 201810579967A CN 108752743 B CN108752743 B CN 108752743B
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- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
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Abstract
A long glass fiber reinforced polypropylene composite material and a preparation method thereof comprise the following steps: mixing polypropylene resin, PP-g-MAH, EMMA, EAA, a polypropylene chain scission agent, an antioxidant and a lubricant, plasticizing by a double-screw extruder, delivering to a soaking machine head, melting and blending with glass fiber, drawing, discharging, and granulating to obtain the long glass fiber reinforced polypropylene composite material. According to the long glass fiber reinforced polypropylene composite material and the preparation method thereof, the condition that the glass fiber bundle is coated by a polypropylene-based melting carrier is effectively avoided by adopting the proper polypropylene, glass fiber, PP-g-MAH, especially EMMA and EAA, and a relatively good processing technology, the dispersion of the glass fiber bundle is effectively reduced on the premise of not influencing the physical property and processing of the long glass fiber reinforced polypropylene composite material, and the formation of glass fiber flocks is avoided by one step, so that an automatic feeding pipeline or a feeding opening is blocked.
Description
Technical Field
The invention relates to a polypropylene composite material, in particular to a long glass fiber reinforced polypropylene composite material and a preparation method thereof, and especially relates to a glass fiber wadding which is not easy to break apart during stirring.
Background
The polypropylene is used as a plastic variety with light weight, no toxicity, acid and alkali resistance and relatively low price, and is widely applied to the fields of building, traffic, agriculture and industry. However, polypropylene has relatively low mechanical properties, and needs to be reinforced by fiber filling, otherwise, it is difficult to meet some occasions with high requirements on mechanical strength. Therefore, it is necessary to improve the strength of mechanical polypropylene by modification means.
Indeed, compared with the ordinary glass fiber reinforced polypropylene, the long glass fiber reinforced polypropylene has higher strength and higher toughness, but has various defects. For example, when the product is injection molded, the surface of the product is easy to have the phenomena that the glass fiber is not dispersed, the surface fiber floats more seriously, and the like. Because of the manufacturing mode, the long glass fiber reinforced polypropylene is formed by soaking the whole glass fiber, plating a layer of polypropylene blending melt, cooling and granulating. Whether the glass fiber bundles are evenly soaked, whether the coating is even and whether the particle cuts are dry and crisp determines whether glass fiber flocks are easy to appear after mixing when a customer uses long glass fiber particles.
When a large part of customers use the long glass fiber reinforced polypropylene, toner and color species are added for color matching; many users also add matrix polypropylene resin or other polypropylene recovery crushing materials in proportion, and use long glass fiber as master batch to improve the overall strength. If the long glass fiber reinforced polypropylene is not well soaked, not well coated and poorly notched long glass fiber particles are easy to disperse during stirring, glass fiber flocks are formed, and pipelines of the automatic feeder, a feed opening of an injection molding machine and the like are often plugged.
Disclosure of Invention
The invention aims to solve the problems in the background art by providing a long glass fiber reinforced polypropylene composite material which is not easy to break glass fiber during stirring and a preparation method thereof, aiming at the problems that the glass fiber is easy to break and form glass fiber flocs which often block the pipeline of an automatic feeder and the feed opening of an injection molding machine to interrupt production when long glass fiber reinforced polypropylene is stirred.
In order to achieve the purpose, the invention provides the following technical scheme: a long glass fiber reinforced polypropylene composite material is composed of the following raw materials in parts by mass:
36.5-65 parts of polypropylene resin, 5-8 parts of PP-g-MAH, 30-50 parts of glass fiber, 0-2 parts of EMMA, 0-2 parts of EAA, 0.1-0.5 part of polypropylene chain scission agent, 0.2-0.5 part of antioxidant and 0.2-0.5 part of lubricant.
Wherein the length of the long glass fiber reinforced polypropylene composite material is 12 mm-13 mm. The melt index of the polypropylene resin is 25g/10 min-80 g/10min at 230 ℃ and under 2.16 kg. The grafting rate of the PP-g-MAH is 0.6 to 0.8 percent. The glass fiber is alkali-free glass fiber direct roving for LFT with the monofilament diameter of 16-17 mu m. EMMA has an MI of 15g/10min and an MMA content of 18%. EAA has MI of 35g/10min and AA content of 18%.
The polypropylene chain scission agent is peroxide. The glass fiber is alkali-free glass fiber which is subjected to surface treatment by a silane coupling agent. The antioxidant is at least one of antioxidants 1010, 168, 1076 and 245; the lubricant is at least one of polyethylene wax, ethylene bis stearamide, calcium stearate and zinc stearate.
The invention also provides a preparation method of the long glass fiber reinforced polypropylene composite material, which comprises the following steps:
step 1): mixing polypropylene resin, PP-g-MAH, EMMA, EAA, a polypropylene chain scission agent, an antioxidant and a lubricant, feeding the mixture into a double-screw extruder, and outputting the mixture to an infiltration machine head;
step 2): the continuous glass fiber auxiliary equipment machine ensures that each glass fiber bundle does not twist by itself and is straightened out, so that the glass fiber bundles can enter the infiltrating machine head after being uniformly opened;
step 3): after the glass fiber is coated from the soaking machine head, the glass fiber is drawn and discharged, and is cut into granules to obtain the long glass fiber reinforced polypropylene composite material, after the glass fiber is sieved, long fiber particles which do not meet the specification are removed, glass fiber silk fibers which possibly appear are removed and enter a finished product bin, and the long glass fiber reinforced polypropylene composite material is obtained after the glass fiber particles and the glass fiber silk fibers are uniformly mixed.
In the step 1), the mixing speed of the mixer is 300 revolutions per minute, and the mixing time is 3 minutes; the processing temperature of the double-screw extruder is 200-220 ℃, the rotating speed of the main machine is 200-400 rpm, and the vacuum degree is more than or equal to 0.08 MPa. The temperature of the infiltrating machine head is 220-240 ℃.
In step 2), the traction speed of the auxiliary machine needs to correspond to the main machine rotating speed in step 1).
In the step 3), the vibrating screen is a linear double-shaft vibrating screen with the aperture of 8 mm.
Compared with the prior art, the invention has the beneficial effects that:
the polypropylene composite material effectively avoids the condition that a melting carrier mainly comprising polypropylene is poor in coating the glass fiber bundles by adopting proper polypropylene, glass fiber, PP-g-MAH, especially EMMA and EAA and a relatively good processing technology, effectively reduces the scattering of the glass fiber bundles on the premise of not influencing the physical property and processing of the long glass fiber reinforced polypropylene composite material, and further avoids the formation of glass fiber flocks to block an automatic feeding pipeline or a feeding port. And has the following characteristics:
1. the adopted related thermoplastic plastics have higher fluidity, low processing temperature, easy dispersion and easy coating of glass fiber.
2. The glass fiber bundle 'relieving-leveling' auxiliary equipment machine is adopted, so that the glass fibers of each bundle are not twisted by themselves, and are leveled and straightened, and the glass fiber bundles can be opened uniformly.
3. The EMMA and EAA are used for increasing the adhesive force of the polypropylene resin, so that the polypropylene and the melting material thereof can more tightly coat the glass fiber.
4. And after being granulated, the mixture passes through a vibrating screen to further remove long fiber particles which do not meet the specification and remove possible glass fiber silk flocs.
Detailed Description
The following examples will explain the present invention in detail, but the present invention is not limited thereto. 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.
The long glass fiber reinforced polypropylene composite material is composed of the following raw materials in parts by mass:
36.5-65 parts of polypropylene resin; 5-8 parts of PP-g-MAH; 30-50 parts of glass fiber; 0-2 parts of EMMA; 0-2 parts of EAA; 0.1-0.5 part of polypropylene chain scission agent; 0.2-0.5 part of antioxidant; 0.2-0.5 part of lubricant.
Wherein the melt index of the polypropylene resin at 230 ℃ under 2.16kg is 25g/10 min-80 g/10 min; the grafting rate of PP-g-MAH is 0.6-0.8%; the glass fiber is alkali-free glass fiber direct roving for LFT with the monofilament diameter of 16-17 mu m; EMMA is 15g/10min MI, MMA content is 18%; EAA is MI 35g/10min, AA content 18%.
The polypropylene chain scission agent is peroxide. The antioxidant is at least one of antioxidants 1010, 168, 1076 and 245. The lubricant is at least one of polyethylene wax, ethylene bis stearamide, calcium stearate and zinc stearate.
The invention also provides a preparation method of the long glass fiber reinforced polypropylene composite material, which comprises the following steps: firstly, mixing polypropylene resin, PP-g-MAH, EMMA, EAA, a polypropylene chain scission agent, an antioxidant and a lubricant in proportion, plasticizing the mixture by a double-screw extruder, delivering the mixture to a soakage machine head to be fused and blended with glass fibers, drawing, discharging and granulating to obtain the long glass fiber reinforced polypropylene composite material.
The method comprises the following specific steps:
step 1) mixing polypropylene resin, PP-g-MAH, EMMA, EAA, a polypropylene chain scission agent, an antioxidant and a lubricant, feeding the mixture into a double-screw extruder, and outputting the mixture to an infiltration machine head;
step 2) a continuous glass fiber auxiliary equipment machine, which prevents each glass fiber bundle from self-twisting and is straightened out, so that the glass fiber bundles can enter a soaking machine head after being uniformly opened;
step 3) after the glass fiber is coated from the soaking machine head, the glass fiber is drawn and discharged, the glass fiber is cut into granules to obtain the long glass fiber reinforced polypropylene composite material, after the glass fiber is sieved by a vibrating screen, the long fiber particles which do not meet the specification are removed, the glass fiber silk fibers which possibly appear are removed and enter a finished product bin, and the glass fiber reinforced polypropylene composite material is obtained after the glass fiber particles and the glass fiber silk fibers are uniformly mixed
In the step 1), the mixing speed of the mixer is 300 revolutions per minute, and the mixing time is 3 minutes; the processing temperature of the double-screw extruder is 200-220 ℃, the rotating speed of the main machine is 200-400 rpm, and the vacuum degree is more than or equal to 0.08 MPa. The temperature of the infiltrating machine head is 220-240 ℃.
In step 2), the traction speed of the auxiliary machine needs to correspond to the main machine rotating speed in step 1).
In the step 3), the vibrating screen is a linear double-shaft vibrating screen with the aperture of 8 mm.
Example 1:
the long glass fiber reinforced polypropylene composite material is prepared from the following raw materials in parts by mass:
36.5 parts of polypropylene resin; 8 parts of PP-g-MAH; 50 parts of glass fiber; 2 parts of EMMA; 2 parts of EAA; 0.5 part of polypropylene chain scission agent; 0.5 part of antioxidant; 0.5 part of lubricant.
Step 1-1), mixing and stirring 36.5 parts of polypropylene resin, 8 parts of PP-g-MAH, 2 parts of EMMA, 2 parts of EAA, 0.5 part of polypropylene chain scission agent, 0.5 part of antioxidant and 0.5 part of lubricant uniformly, adding the mixture into a double-screw extruder from a main feeding port, and outputting the mixture to an infiltration machine head;
correspondingly to the step (1-1), the step 2-1) is that 50 parts of glass fiber is not twisted by self and is leveled and straightened by a continuous glass fiber auxiliary equipment machine and enters an infiltration machine head;
and 3-1) coating the glass fibers from the soaking machine head, drawing, discharging, granulating to obtain the long glass fiber reinforced polypropylene composite material, removing long fiber particles which do not meet the specification after passing through a vibrating screen, removing glass fiber silk flocs which possibly appear, entering a finished product bin, and uniformly mixing to obtain the long glass fiber reinforced polypropylene composite material.
Example 2:
the long glass fiber reinforced polypropylene composite material is prepared from the following raw materials in parts by mass:
62.5 parts of polypropylene resin; 5 parts of PP-g-MAH; 30 parts of glass fiber; 2 parts of EMMA; 2 parts of EAA; 0.1 part of polypropylene chain scission agent; 0.2 part of antioxidant; 0.2 part of lubricant.
Step 1-2), mixing and stirring 62.5 parts of polypropylene resin, 5 parts of PP-g-MAH, 2 parts of EMMA, 2 parts of EAA, 0.1 part of polypropylene chain scission agent, 0.2 part of antioxidant and 0.2 part of lubricant uniformly, adding the mixture into a double-screw extruder from a main feeding port, and outputting the mixture to an infiltration machine head;
correspondingly to the step 1-2), the step 2-2) is corresponding to the step 1-2), and 30 parts of glass fiber is enabled not to be twisted by self and to be leveled and straightened by passing through a continuous glass fiber auxiliary equipment machine, and then enters an infiltration machine head;
and 3-2) coating the glass fibers from the soaking machine head, drawing, discharging, granulating to obtain the long glass fiber reinforced polypropylene composite material, removing long fiber particles which do not meet the specification after passing through a vibrating screen, removing glass fiber silk flocs which possibly appear, entering a finished product bin, and uniformly mixing to obtain the long glass fiber reinforced polypropylene composite material.
Comparative example 1:
the only difference between the method and example 1 is that no EMMA or EAA is added.
Comparative example 2:
the only difference between the method and example 2 is that no EMMA or EAA is added.
The main performance and warpage comparison results of the polypropylene materials of examples 1-2 and comparative examples 1-2 are shown in Table 1.
TABLE 1 comparison of the Properties of the Polypropylene materials of the examples and comparative examples
Note 1: the stirring test was carried out by using a mixer at a rotation speed of 300 rpm, stirring for 3 minutes and then visually observing.
From a summary of the test data in table 1 it can be seen that:
the total amount of EMMA and EAA is within 4 percent, so that the rigidity and toughness of the material are not obviously influenced;
the influence of EMMA and EAA is greater on the composite material with high glass fiber content than on the composite material with low glass fiber content;
in the composite material with lower glass fiber content, the glass fiber has better coating effect and thicker coating layer, so that no EMMA or EAA is added, and the glass fiber silk flock can not be obviously dispersed;
therefore, the long glass fiber reinforced polypropylene composite material which is not easy to disperse glass fiber flocks during stirring, obtained by the invention, does not influence the mechanical properties of the original material, and effectively solves the problem that the long glass fiber reinforced polypropylene composite material with high glass fiber content is easy to generate glass fiber flocks to be separated after being stirred and used, so that the problem that a feeding pipe of an automatic feeding device and a discharging opening of an injection molding machine are blocked further is solved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. The long glass fiber reinforced polypropylene composite material is characterized by comprising the following raw materials in parts by mass:
36.5-65 parts of polypropylene resin, 5-8 parts of PP-g-MAH, 30-50 parts of glass fiber, 2 parts of EMMA, 2 parts of EAA, 0.1-0.5 part of polypropylene chain scission agent, 0.2-0.5 part of antioxidant and 0.2-0.5 part of lubricant;
the long glass fiber reinforced polypropylene composite material is 12-13 mm in length, and the glass fiber is alkali-free glass fiber direct roving for LFT with the monofilament diameter of 16-17 mu m;
the melt index of the polypropylene resin at 230 ℃ under 2.16kg is 25g/10 min-80 g/10 min; the grafting rate of the PP-g-MAH is 0.6-0.8%; the MI of the EMMA is 15g/10min, and the MMA content is 18%; the MI of EAA is 35g/10min, and the AA content is 18%;
the polypropylene chain scission agent is peroxide;
the glass fiber is alkali-free glass fiber subjected to surface treatment by a silane coupling agent;
the antioxidant is at least one of antioxidants 1010, 168, 1076 and 245; the lubricant is at least one of calcium stearate or zinc stearate.
2. The preparation method of the long glass fiber reinforced polypropylene composite material according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
s1: firstly, mixing polypropylene resin, PP-g-MAH, EMMA, EAA, a polypropylene chain scission agent, an antioxidant and a lubricant in proportion, feeding the mixture into a double-screw extruder, and outputting the mixture to an infiltration machine head;
s2: the continuous glass fiber auxiliary equipment machine ensures that each glass fiber bundle does not twist by itself and is straightened out, so that the glass fiber bundles can enter the infiltrating machine head after being uniformly opened;
s3: after the glass fiber is coated from the wetting machine head, the glass fiber is drawn, discharged and cut into particles to obtain a long glass fiber reinforced polypropylene composite material, after the long glass fiber reinforced polypropylene composite material passes through a vibrating screen, long fiber particles which do not meet the specification are removed, glass fiber silk fibers which possibly appear are removed and enter a finished product bin, and the long glass fiber reinforced polypropylene composite material is obtained after the long glass fiber reinforced polypropylene composite material is uniformly mixed;
in S1, the mixing speed of the mixer is 300 r/min, and the mixing time is 3 min; the processing temperature of the double-screw extruder is 200-220 ℃, the rotating speed of the main machine is 200-400 rpm, and the vacuum degree is more than or equal to 0.08 MPa; the temperature of the infiltrating machine head is 220-240 ℃;
in S2, the traction speed of the auxiliary machine needs to correspond to the main machine rotation speed in S1;
in S3, the vibrating screen is a linear double-shaft vibrating screen with the aperture of 8 mm.
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|---|---|---|---|---|
| CN101338051A (en) * | 2008-08-08 | 2009-01-07 | 苏州工业园区和昌电器有限公司 | Long glass fiber reinforced polypropylene material and preparation thereof |
| CN103183894A (en) * | 2011-12-29 | 2013-07-03 | 辽宁辽杰科技有限公司 | Continuous glass fiber reinforced polypropylene resin composite material and preparation method thereof |
| CN103589103A (en) * | 2012-08-14 | 2014-02-19 | 合肥杰事杰新材料股份有限公司 | Long glass fiber reinforced composite polypropylene material, and preparation method and application thereof |
| CN104910517A (en) * | 2015-06-15 | 2015-09-16 | 上海俊尓新材料有限公司 | Bimodally-distributed glass fiber reinforced polypropylene composite material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338051A (en) * | 2008-08-08 | 2009-01-07 | 苏州工业园区和昌电器有限公司 | Long glass fiber reinforced polypropylene material and preparation thereof |
| CN103183894A (en) * | 2011-12-29 | 2013-07-03 | 辽宁辽杰科技有限公司 | Continuous glass fiber reinforced polypropylene resin composite material and preparation method thereof |
| CN103589103A (en) * | 2012-08-14 | 2014-02-19 | 合肥杰事杰新材料股份有限公司 | Long glass fiber reinforced composite polypropylene material, and preparation method and application thereof |
| CN104910517A (en) * | 2015-06-15 | 2015-09-16 | 上海俊尓新材料有限公司 | Bimodally-distributed glass fiber reinforced polypropylene composite material and preparation method thereof |
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