CN113444269A - Low-warpage good-appearance glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Low-warpage good-appearance glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 50
- -1 polypropylene Polymers 0.000 title claims abstract description 47
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 46
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002678 cellulose Polymers 0.000 claims abstract description 27
- 239000001913 cellulose Substances 0.000 claims abstract description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 3
- 239000005043 ethylene-methyl acrylate Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007667 floating Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a low-warpage good-appearance glass fiber reinforced polypropylene composite material and a preparation method thereof, wherein the composite material is prepared from the following components in parts by weight: 30-75 parts of polypropylene, 20-40 parts of glass fiber, 2-8 parts of compatilizer, 2-10 parts of flexibilizer, 2-10 parts of modified nano cellulose and 0.5-2 parts of auxiliary agent; the modified nano-cellulose is obtained by treating with silane coupling agent. According to the invention, through the synergistic effect of the toughening agent and the modified nano-cellulose, the buckling deformation phenomenon of the traditional glass fiber reinforced polypropylene can be effectively improved, and the glass fiber reinforced polypropylene has good mechanical properties and excellent appearance effect. The nano-cellulose has excellent mechanical properties and stable chemical properties, the silane coupling agent is used for modifying the nano-cellulose, the dispersibility of the nano-cellulose in polypropylene is improved, and meanwhile, a hydrocarbon chain provided by the silane coupling agent and the nano-cellulose can form a cross-linked network, so that the overall performance of the material is further enhanced.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-warpage good-appearance glass fiber reinforced polypropylene composite material and a preparation method thereof.
Background
The polypropylene is one of five general-purpose plastics, has excellent comprehensive properties such as light weight, low water absorption, wide processing technological conditions and the like, and is widely applied to the fields of daily necessities such as automobiles, household appliances and the like; in the actual use process, in order to further improve the mechanical strength of the polypropylene material, the filled glass fiber is adopted for reinforcement modification, the rigidity strength of the polypropylene material reinforced and modified by the glass fiber is obviously improved, but the glass fiber belongs to a needle-shaped structure, has extremely high length-diameter ratio and different orientation degrees in a product, so that the shrinkage rate of the polypropylene material in the flow direction and the vertical direction in the injection molding process is greatly different, and the obvious anisotropic difference can cause the material to generate serious warping deformation; in addition, because the compatibility between the glass fiber and the polypropylene resin matrix is poor, the appearance state of the product is poor, and the factors limit the application of the material in some special fields.
In order to improve the diversified application of the glass fiber reinforced polypropylene material, research institutions at home and abroad make researches in many aspects, and the currently effective method is to reduce the orientation of the terminal material by using flat glass fibers, for example, the Chinese patent CN201710250325 uses the flat glass fibers to reduce the warping deformation; however, the flat glass fiber has high cost, so that the popularization and the application of the flat glass fiber are limited. The chinese invention patent CN102070843A discloses that the batch mixing of long glass fiber reinforced polypropylene masterbatch and high impact resistant low floating fiber masterbatch is used to produce high impact resistant low floating fiber long glass fiber reinforced material, which can improve the apparent state of long glass fiber reinforced material, but does not relate to the problem of surface floating fiber of chopped glass fiber and continuous glass fiber reinforced polypropylene composite material.
Therefore, it is necessary to develop a glass fiber reinforced material with low cost, low warpage and good appearance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a glass fiber reinforced polypropylene composite material with low warpage and good appearance and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the glass fiber reinforced polypropylene composite material with low warpage and good appearance is characterized in that: the composition is prepared from the following components in parts by weight:
the modified nano-cellulose is nano-cellulose obtained by treatment of a silane coupling agent.
Preferably, the melt index of the polypropylene is 5-100 g/10min at 230 ℃ under the condition of 2.16 kg.
Preferably, the glass fiber is alkali-free glass fiber treated by a silane coupling agent; the mass ratio of the glass fiber to the silane coupling agent is (23-30): 1. more preferably, the silane coupling agent is at least one of KH-550, KH-560, KH-570, A-151 and A-171.
Preferably, the compatilizer is at least one of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer, and ethylene-methyl acrylate maleic anhydride copolymer. The toughening agent is at least one of POE, PE and SEBS. The auxiliary agent comprises at least one of an antioxidant, a lubricant, a UV resistant agent and a pigment.
Preferably, the preparation method of the modified nanocellulose comprises the following steps: dispersing the nano-cellulose and a silane coupling agent in an ethanol water solution, stirring for 1-2h, performing suction filtration to obtain a solid substance, and drying to obtain the modified nano-cellulose.
The invention also aims to provide a preparation method of the glass fiber reinforced polypropylene composite material with low warpage and good appearance, which comprises the following steps: after weighing the components according to the proportion, adding the polypropylene, the compatilizer, the toughening agent, the modified nano cellulose and the auxiliary agent into a double-screw extruder from a main feeding port, adding the glass fiber into the double-screw extruder from a side feeding port, and carrying out melting, extrusion and granulation to obtain the low-warpage and good-appearance glass fiber reinforced polypropylene composite material.
Compared with the prior art, the invention has the beneficial effects that:
the nano-cellulose has excellent mechanical properties, high crystallinity, low density and stable chemical properties, but the surface of the unmodified nano-cellulose is rich in hydroxyl and has larger polarity, so that the compatibility between the nano-cellulose and a polypropylene matrix is poor, and the nano-cellulose is difficult to uniformly disperse in polypropylene; according to the invention, the silane coupling agent is used for modifying the nano-cellulose, so that on one hand, the silane coupling agent can replace hydroxyl on the surface of the nano-cellulose to reduce the polarity of the nano-cellulose, and the nano-cellulose can be uniformly dispersed in a polypropylene matrix; on the other hand, the hydrocarbon chain provided by the silane coupling agent can form a cross-linked network with the nanocellulose, so that the overall performance of the material is further enhanced.
According to the invention, through the synergistic effect of the toughening agent and the modified nano-cellulose, the buckling deformation phenomenon of the traditional glass fiber reinforced polypropylene can be effectively improved, and the glass fiber reinforced polypropylene has good mechanical properties and excellent appearance effect.
Detailed Description
The present invention is further described below, and the following examples are only for illustrating the technical solutions of the present invention more clearly, and are not intended to limit the technical scope of the present invention.
In the following examples and comparative examples, the following starting materials were used:
polypropylene, brand number M60RHC, manufactured by zhenhai refining chemical company, china petrochemical company limited;
glass fiber, 248A, manufactured by Shanghai Branch of Ohwi Kening (China) Co., Ltd;
maleic anhydride grafted polypropylene, grade CA100, manufactured by arkema corporation, france;
maleic anhydride grafted ethylene-octene copolymer, No. 493D, manufactured by dupont, usa;
ethylene-methyl acrylate maleic anhydride copolymer, having a designation AX-4700, manufactured by Arkema, France;
POE, the number is POE 8730L, and the manufacturer is Korea SK group;
SEBS with the brand number of SEBS 6154 is produced by Taiwan rubber company Limited in Taiwan;
the lubricant is polyethylene wax.
Other materials are common products sold in the market;
the reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
A preparation method of a glass fiber reinforced polypropylene composite material with low warpage and good appearance comprises the following steps: after weighing the components according to the raw material ratio in table 1, adding the polypropylene, the compatilizer, the toughening agent, the modified nanocellulose and the auxiliary agent into a double-screw extruder from a main feeding port, and adding the glass fiber into the double-screw extruder from a side feeding port, wherein the processing parameters of the double-screw extruder are as follows: the diameter of the screw is 20mm, and the length-diameter ratio of the screw is 40: 1, the processing temperature of each section is as follows: the first section is 1850 ℃, the second section is 190 ℃, the third section is 195 ℃, the fourth section is 200 ℃, the fifth section is 210 ℃, the melt temperature is 205 ℃, and the head temperature is 215 ℃; and melting, extruding and granulating to obtain the glass fiber reinforced polypropylene composite material with low warpage and good appearance.
Wherein the glass fiber is mixed with KH-550 according to the mass ratio of 25:1 before being added into the side feeding port. The preparation method of the modified nano-cellulose comprises the following steps: dispersing nano-cellulose and KH-550 in 95% ethanol aqueous solution according to the mass ratio of 10:1, stirring for 1.5h, performing suction filtration to obtain solid matter, and drying to obtain the modified nano-cellulose.
TABLE 1 formulation Components of examples 1-5 and comparative examples 1-3
And (3) performance detection:
the products from the examples and comparative examples were tested for performance according to the test criteria in table 2:
table 2 shows the test conditions and standards
| Test items | Standard of merit | Condition | Sample specification |
| Tensile strength | ISO 527 | 23℃，50mm/min | Dumbbell-shaped splines 115 x 10 x 4mm |
| Bending strength | ISO 178 | 23℃，50mm/min | Rectangular splines 80 x 10 x 4mm |
| Flexural modulus | ISO 178 | 23℃，50mm/min | Rectangular splines 80 x 10 x 4mm |
| State of floating fiber | Visualization | / | Circular sheet with thickness of 2mm |
| Degree of warp | / | / | Circular sheet with thickness of 2mm |
Note: the fiber-floating state is judged by visual observation, the poor represents the poor appearance state, and the larger the number of the poor represents the poorer the appearance of the material; "excellent" represents good superficial fiber state of appearance, and the larger the number of excellent "represents the better appearance of the material; the warping degree test method comprises the following steps: and fixing one end of the obtained circular sheet on a plane, and measuring the height difference between the vertex of the other end and the plane to obtain the warping degree.
The results are shown in table 3:
TABLE 3 test results of examples 1 to 5 and comparative examples 1 to 3
According to the above examples and comparative examples, the mechanical properties of the glass fiber reinforced polypropylene composite material compounded by adding the toughening agent and the modified nanocellulose are less different from those of the conventional glass fiber reinforced polypropylene composite material, but the glass fiber reinforced polypropylene composite material has more excellent appearance and lower warping degree. It is suitable for various engineering plastic parts for automobiles and household electrical appliances.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The glass fiber reinforced polypropylene composite material with low warpage and good appearance is characterized in that: the composition is prepared from the following components in parts by weight:
the modified nano-cellulose is nano-cellulose obtained by treatment of a silane coupling agent.
2. The low warpage good appearance glass fiber reinforced polypropylene composite material according to claim 1, wherein: the melt index of the polypropylene is 5-100 g/10min at 230 ℃ under the condition of 2.16 kg.
3. The low warpage good appearance glass fiber reinforced polypropylene composite material according to claim 1, wherein: the glass fiber is alkali-free glass fiber treated by a silane coupling agent; the mass ratio of the glass fiber to the silane coupling agent is (23-30): 1.
4. the low warpage good appearance glass fiber reinforced polypropylene composite material according to claim 3, wherein: the silane coupling agent is at least one of KH-550, KH-560, KH-570, A-151 and A-171.
5. The low warpage good appearance glass fiber reinforced polypropylene composite material according to claim 1, wherein: the compatilizer is at least one of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer and ethylene-methyl acrylate maleic anhydride copolymer.
6. The low warpage good appearance glass fiber reinforced polypropylene composite material according to claim 1, wherein: the toughening agent is at least one of POE, PE and SEBS.
7. The low warpage good appearance glass fiber reinforced polypropylene composite material according to claim 1, wherein: the auxiliary agent comprises at least one of an antioxidant, a lubricant, a UV resistant agent and a pigment.
8. The low warpage good appearance glass fiber reinforced polypropylene composite material according to claim 1, wherein: the preparation method of the modified nano-cellulose comprises the following steps: dispersing the nano-cellulose and a silane coupling agent in an ethanol water solution, stirring for 1-2h, performing suction filtration to obtain a solid substance, and drying to obtain the modified nano-cellulose.
9. The preparation method of the glass fiber reinforced polypropylene composite material with low warpage and good appearance according to any one of claims 1 to 8, wherein the preparation method comprises the following steps: the method comprises the following steps: after weighing the components according to the proportion, adding the polypropylene, the compatilizer, the toughening agent, the modified nano cellulose and the auxiliary agent into a double-screw extruder from a main feeding port, adding the glass fiber into the double-screw extruder from a side feeding port, and carrying out melting, extrusion and granulation to obtain the low-warpage and good-appearance glass fiber reinforced polypropylene composite material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110769388.1A CN113444269A (en) | 2021-07-07 | 2021-07-07 | Low-warpage good-appearance glass fiber reinforced polypropylene composite material and preparation method thereof |
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| CN202110769388.1A CN113444269A (en) | 2021-07-07 | 2021-07-07 | Low-warpage good-appearance glass fiber reinforced polypropylene composite material and preparation method thereof |
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| CN114605739A (en) * | 2022-03-28 | 2022-06-10 | 金发科技股份有限公司 | Nanofiber modified PP composite material and preparation method and application thereof |
| CN115353687A (en) * | 2022-09-30 | 2022-11-18 | 金发科技股份有限公司 | Cellulose reinforced polypropylene composition and preparation method and application thereof |
| CN115947992A (en) * | 2022-12-28 | 2023-04-11 | 上海日之升科技有限公司 | Wheat straw powder polypropylene wood-plastic composite material and preparation method thereof |
| CN116120661A (en) * | 2022-12-27 | 2023-05-16 | 金发科技股份有限公司 | Composite fiber modified PP material and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605739A (en) * | 2022-03-28 | 2022-06-10 | 金发科技股份有限公司 | Nanofiber modified PP composite material and preparation method and application thereof |
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| CN115947992A (en) * | 2022-12-28 | 2023-04-11 | 上海日之升科技有限公司 | Wheat straw powder polypropylene wood-plastic composite material and preparation method thereof |
| CN115947992B (en) * | 2022-12-28 | 2024-02-20 | 上海日之升科技有限公司 | Wheat straw powder polypropylene wood-plastic composite material and preparation method thereof |
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