CN113444314A - Glass fiber reinforced polypropylene material and preparation method and application thereof - Google Patents
Glass fiber reinforced polypropylene material and preparation method and application thereof Download PDFInfo
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- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention discloses a glass fiber reinforced polypropylene material and a preparation method and application thereof, wherein the glass fiber reinforced polypropylene material is prepared from 58.2-89.3 parts of polypropylene, 10-40 parts of modified glass fiber, 0.2-0.8 part of antioxidant and 0.5-1 part of lubricant according to parts by mass, wherein the modified glass fiber is polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate grafted glass fiber. The glass fiber reinforced polypropylene material can reduce the poor warping condition of the glass fiber reinforced polypropylene material.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a glass fiber reinforced polypropylene material and a preparation method and application thereof.
Background
Because of its excellent performance and low price, polypropylene is widely used in the fields of automobiles, household electrical appliances, electronic and electrical appliances, etc. Meanwhile, the glass fiber reinforced polypropylene material has obviously improved rigidity, impact property and temperature resistance due to the addition of the glass fiber, so that the glass fiber reinforced polypropylene material is widely applied to structural members needing strength requirements in the fields. However, the glass fiber has a large aspect ratio, and thus the glass fiber is likely to cause uneven orientation in the matrix, resulting in warping of the product and thus affecting the use.
Disclosure of Invention
In view of the above, the present invention provides a glass fiber reinforced polypropylene material, and a preparation method and an application thereof, in the present invention, a grafting modification is performed on glass fibers, so that a cluster-like elastic polymer chain is formed on the surface of the glass fibers, and the directional orientation ratio of the glass fibers is reduced in the injection molding process of the material, thereby effectively reducing the poor warping condition of the glass fiber reinforced polypropylene material, and solving the warping problem of the existing glass fiber reinforced polypropylene material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a glass fiber reinforced polypropylene material, which is prepared from 58.2-89.3 parts of polypropylene, 10-40 parts of modified glass fiber, 0.2-0.8 part of antioxidant and 0.5-1 part of lubricant in parts by mass, wherein the modified glass fiber is polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate grafted glass fiber.
Further, the polypropylene is one or a mixture of two of polypropylene copolymer and polypropylene homopolymer.
Further, the antioxidant is one or a mixture of two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite.
Further, the lubricant is one or a mixture of more than two of ethylene bis-hard amide, pentaerythritol stearate and silicone powder.
Further, the specific preparation method of the modified glass fiber comprises the following steps:
the mass ratio of polyethylene glycol monomethyl ether, 3- (triethoxysilyl) propyl isocyanate and methyldiethanolamine is 1 (0.02-0.05): (0.01-0.015) adding the mixture into dichloromethane, carrying out reflux reaction for 24-48 hours at 50-60 ℃ under the protection of inert gas or nitrogen, filtering and drying to obtain polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate;
polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanic acid and glass fiber are mixed according to the mass ratio of 1: (20-30) adding the mixture into distilled water, heating the mixture to 60-80 ℃ under the protection of inert gas or nitrogen, reacting for 24-48 hours, filtering and drying to obtain the modified glass fiber. The specific reaction process is as follows:
preferably, the glass fibers are chopped glass fibers.
In a second aspect of the present invention, there is disclosed a method for preparing a glass fiber reinforced polypropylene material according to the first aspect of the present invention, comprising the steps of:
and fully and uniformly mixing the polypropylene, the antioxidant, the lubricant and the coupling agent according to the proportion, adding the mixture into a double-screw extruder from a main material port, simultaneously adding the modified glass fiber from a side feeding port, and performing melt extrusion, granulation and drying to obtain the glass fiber reinforced polypropylene material.
Further, the rotation speed of the main machine of the double-screw extruder is 280-400rpm, and the temperature in the machine barrel is 180-230 ℃.
The third aspect of the invention discloses the application of the glass fiber reinforced polypropylene material in the first aspect of the invention in preparing automotive interior parts.
The invention provides a method for preparing a modified glass fiber by grafting 3- (triethoxysilyl) propyl isocyanic acid onto polyethylene glycol, wherein the polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate grafted glass fiber is used as the modified glass fiber, and a cluster-shaped elastic macromolecular chain is formed on the surface of the glass fiber, so that the bonding force between the glass fiber and a substrate is enhanced, the mechanical property of the material can be improved, and the use of the traditional compatilizer PP-G can be avoided, so that the odor property of the glass fiber product is improved, the defect of large odor of the traditional glass fiber product is overcome, and the modified glass fiber can be applied to automotive interior trim. The cluster-shaped elastic macromolecular chains are formed on the surface of the glass fiber, the proportion of the oriented orientation of the glass fiber is reduced in the process of injection molding of the material due to the effect of steric hindrance, and the cluster-shaped elastic macromolecular chains on the surface layer can deform according to the crystallization process in the process of crystallization of the matrix polypropylene so as to reduce residual stress and effectively reduce the poor warping condition of the glass fiber reinforced polypropylene material.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The polypropylene is preferably PP EA5076 Basel, PP T30S medium petrochemical, PP 8285E1 Exxomeifu
The glass fiber is preferably glass fiber-305K-3.0 Chongqing International; glass fiber-248A Owensikoning
Polyethylene glycol monomethyl ether, 3- (triethoxysilyl) propyl isocyanate, methyldiethanolamine and dichloromethane are all commercially available analytical reagents, namely avastin reagent
The antioxidant is preferably 1010, 168 basf
The lubricant is preferably ethylene bis-hard amide, silicone E525, Winddrive.
Example 1
Weighing 68.7 parts of polypropylene PP EA5076, 30 parts of modified fiber, 0.2 part of antioxidant 1010, 0.3 part of antioxidant 168 and 0.8 part of lubricant ethylene bis-stearamide in parts by weight, uniformly mixing the polypropylene, the antioxidant and the lubricant, adding the mixture into a double-screw extruder from a main material port, simultaneously adding the modified glass fiber into the double-screw extruder from a side feeding port, controlling the rotating speed of a main machine of the double-screw extruder to be 320rpm, and controlling the processing temperature of each zone of the double-screw extruder to be: the temperature in the first zone is 180 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 200 ℃, the temperature in the fourth zone is 210 ℃ and the temperature in the fifth zone is 200 ℃.
The preparation method of the modified fiber in the embodiment comprises the following steps: adding 1g of polyethylene glycol monomethyl ether, 0.03g of 3- (triethoxysilyl) propyl isocyanate and 0.012g of methyldiethanolamine into dichloromethane, carrying out reflux reaction for 40 hours at 55 ℃ under the protection of helium, and filtering and drying the obtained product; adding 1g of the product and 25g of chopped glass fiber-305K-3.0 into distilled water, and heating to 70 ℃ under the protection of helium to react for 40 hours to obtain the glass fiber reinforced plastic.
Example 2
Weighing 78.9 parts of polypropylene PP T30S, 20 parts of modified fiber, 0.4 part of antioxidant 1010 and 0.7 part of lubricant ethylene bis-stearamide according to parts by weight, uniformly mixing polypropylene, antioxidant and lubricant, adding the mixture into a double-screw extruder from a main material port, adding modified glass fiber from a side feeding port, controlling the rotating speed of a main machine of the double-screw extruder to be 360rpm, and controlling the processing temperature of each zone of the double-screw extruder to be: the temperature in the first zone is 180 ℃, the temperature in the second zone is 185 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 200 ℃ and the temperature in the fifth zone is 210 ℃.
The preparation method of the modified fiber in the embodiment comprises the following steps: adding 20g of polyethylene glycol monomethyl ether, 0.8g of 3- (triethoxysilyl) propyl isocyanate and 0.28g of methyldiethanolamine into dichloromethane, carrying out reflux reaction for 35 hours at 58 ℃ under the protection of helium, and filtering and drying the obtained product; adding 10g of the product and 230g of chopped glass fiber glass-248A into distilled water, and heating to 65 ℃ under the protection of helium to react for 26 hours to obtain the glass fiber reinforced plastic.
Example 3
Weighing 83.8 parts of polypropylene PP 8285E1, 15 parts of modified fiber, 0.3 part of antioxidant 1010, 0.3 part of antioxidant 168 and 0.6 part of lubricant silicone E525 according to parts by weight, uniformly mixing the polypropylene, the antioxidant and the lubricant, adding the mixture into a double-screw extruder from a main material port, simultaneously adding the modified glass fiber into the double-screw extruder from a side feeding port, controlling the main machine rotating speed of the double-screw extruder to be 380rpm, and controlling the processing temperature of each zone of the double-screw extruder to be: the temperature in the first zone was 200 deg.C, the temperature in the second zone was 210 deg.C, the temperature in the third zone was 210 deg.C, the temperature in the fourth zone was 220 deg.C, and the temperature in the fifth zone was 220 deg.C.
The preparation method of the modified fiber in the embodiment comprises the following steps: adding 26g of polyethylene glycol monomethyl ether, 0.78g of 3- (triethoxysilyl) propyl isocyanate and 0.338g of methyldiethanolamine into dichloromethane, carrying out reflux reaction for 45 hours at 58 ℃ under the protection of helium, and filtering and drying the obtained product; adding 25g of the product and 700g of chopped glass fiber-305K-3.0 into distilled water, and heating to 75 ℃ under the protection of helium to react for 45 hours to obtain the glass fiber reinforced plastic.
Example 4
Weighing 89.3 parts of polypropylene PP 8285E1, 10 parts of modified fiber, 0.2 part of antioxidant 168 and 0.5 part of lubricant silicone E525 according to parts by weight, uniformly mixing the polypropylene, the antioxidant and the lubricant, adding the mixture into a double-screw extruder from a main material port, adding the modified glass fiber from a side feeding port, controlling the rotating speed of a main machine of the double-screw extruder to be 280rpm, and controlling the processing temperature of each zone of the double-screw extruder to be: the temperature in the first zone is 210 ℃, the temperature in the second zone is 210 ℃, the temperature in the third zone is 220 ℃, the temperature in the fourth zone is 220 ℃ and the temperature in the fifth zone is 230 ℃.
The preparation method of the modified fiber in the embodiment comprises the following steps: adding 12g of polyethylene glycol monomethyl ether, 0.24g of 3- (triethoxysilyl) propyl isocyanate and 0.12g of methyldiethanolamine into dichloromethane, carrying out reflux reaction for 24 hours at 50 ℃ under the protection of helium, and filtering and drying the obtained product; adding 10g of the product and 200g of chopped glass fiber-305K-3.0 into distilled water, and heating to 60 ℃ under the protection of helium to react for 24 hours to obtain the glass fiber reinforced plastic.
Example 5
Weighing 58.2 parts of polypropylene PP EA5076, 40 parts of modified fiber, 0.4 part of antioxidant 1010, 0.4 part of antioxidant 168 and 1 part of lubricant silicone E525 in parts by weight, uniformly mixing polypropylene, antioxidant and lubricant, adding the mixture into a double-screw extruder from a main material port, adding modified glass fiber into the double-screw extruder from a side feeding port, controlling the rotating speed of a main machine of the double-screw extruder to be 400rpm, and controlling the processing temperature of each zone of the double-screw extruder to be: the temperature in the first zone was 190 ℃, the temperature in the second zone was 195 ℃, the temperature in the third zone was 200 ℃, the temperature in the fourth zone was 200 ℃ and the temperature in the fifth zone was 210 ℃.
The preparation method of the modified fiber in the embodiment comprises the following steps: adding 30g of polyethylene glycol monomethyl ether, 1.5g of 3- (triethoxysilyl) propyl isocyanate and 0.45g of methyldiethanolamine into dichloromethane, carrying out reflux reaction for 48 hours at 60 ℃ under the protection of helium, and filtering and drying the obtained product; adding 20g of the product and 600g of chopped glass fiber glass-248A into distilled water, and heating to 80 ℃ under the protection of helium to react for 48 hours to obtain the glass fiber reinforced plastic.
Comparative example 1
Weighing 73.9 parts of polypropylene PP EA5076, 20 parts of glass fiber-305K-3.0, 5 parts of PP-G grafted maleic anhydride, 0.2 part of antioxidant 1010, 0.3 part of antioxidant 168 and 0.6 part of lubricant silicone E525 according to parts by weight, uniformly mixing polypropylene, antioxidant and lubricant, adding the mixture into a double-screw extruder from a main material port, simultaneously adding glass fiber from a side feeding port, controlling the main machine rotation speed of the double-screw extruder to be 260rpm, and controlling the processing temperature of each zone of the double-screw extruder to be: the temperature in the first zone is 180 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 200 ℃, the temperature in the fourth zone is 210 ℃ and the temperature in the fifth zone is 200 ℃.
Comparative example 2
Weighing 60.9 parts of polypropylene PP T30S, 30 parts of glass fiber-248A, 8 parts of PP-G grafted maleic anhydride, 0.2 part of antioxidant 1010, 0.3 part of antioxidant 168 and 0.6 part of lubricant ethylene bis-hard amide according to parts by weight, uniformly mixing polypropylene, antioxidant and lubricant, adding the mixture into a double-screw extruder from a main material port, simultaneously adding glass fiber from a side feeding port, controlling the main machine rotation speed of the double-screw extruder to be 260rpm, and controlling the processing temperature of each zone of the double-screw extruder to be: the temperature in the first zone is 180 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 200 ℃, the temperature in the fourth zone is 210 ℃ and the temperature in the fifth zone is 200 ℃.
The glass fiber reinforced polypropylene materials prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to a correlation performance test, and the results are shown in table 1:
TABLE 1 results of performance test of glass fiber reinforced polypropylene materials in examples and comparative examples
From the test results in table 1, it can be seen that the modified polypropylene prepared from the polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate grafted glass fiber modified reinforced polypropylene material of the present invention has higher strength and impact property and more excellent mechanical properties than the conventional glass fiber reinforced polypropylene material. The finished piece is flat and has no warping condition and better smell.
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 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 (9)
1. The glass fiber reinforced polypropylene material is characterized by being prepared from 58.2-89.3 parts of polypropylene, 10-40 parts of modified glass fiber, 0.2-0.8 part of antioxidant and 0.5-1 part of lubricant according to parts by mass, wherein the modified glass fiber is polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate grafted glass fiber.
2. The glass fiber reinforced polypropylene material of claim 1, wherein the polypropylene is one or a mixture of a co-polypropylene and a homo-polypropylene.
3. The glass fiber reinforced polypropylene material of claim 1, wherein the antioxidant is one or a mixture of two of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite.
4. The glass fiber reinforced polypropylene material according to claim 1, wherein the lubricant is one or a mixture of two or more of ethylene bis-stearamide, pentaerythritol stearate and silicone powder.
5. The glass fiber reinforced polypropylene material according to claim 1, wherein the modified glass fiber is prepared by a specific method comprising the following steps:
the mass ratio of polyethylene glycol monomethyl ether, 3- (triethoxysilyl) propyl isocyanate and methyldiethanolamine is 1 (0.02-0.05): (0.01-0.015) adding the mixture into dichloromethane, carrying out reflux reaction for 24-48 hours at 50-60 ℃ under the protection of inert gas or nitrogen, filtering and drying to obtain polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanate;
polyethylene glycol grafted 3- (triethoxysilyl) propyl isocyanic acid and glass fiber are mixed according to the mass ratio of 1: (20-30) adding the mixture into distilled water, heating the mixture to 60-80 ℃ under the protection of inert gas or nitrogen, reacting for 24-48 hours, filtering and drying to obtain the modified glass fiber.
6. The glass-fiber reinforced polypropylene material of claim 5, wherein the glass fibers are chopped glass fibers.
7. A process for the preparation of a glass fiber reinforced polypropylene material according to any one of claims 1 to 6, comprising the steps of:
and fully and uniformly mixing the polypropylene, the antioxidant and the lubricant according to the proportion, adding the mixture into a double-screw extruder from a main material port, simultaneously adding the modified glass fiber from a side feeding port, and performing melt extrusion, granulation and drying to obtain the glass fiber reinforced polypropylene material.
8. The method as claimed in claim 7, wherein the rotation speed of the main machine of the twin-screw extruder is 280-400rpm, and the temperature in the barrel is 180-230 ℃.
9. Use of a glass fiber reinforced polypropylene material according to any one of claims 1 to 6 for the preparation of automotive interior trim parts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115895118A (en) * | 2022-12-08 | 2023-04-04 | 安庆会通新材料有限公司 | Solvent-resistant floating fiber reinforced polypropylene material, preparation method and application |
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| CN115895118B (en) * | 2022-12-08 | 2024-03-12 | 安庆会通新材料有限公司 | Solvent-resistant floating fiber reinforced polypropylene material, preparation method and application |
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