CN113667214B - Continuous fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Continuous fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN113667214B CN113667214B CN202110865154.7A CN202110865154A CN113667214B CN 113667214 B CN113667214 B CN 113667214B CN 202110865154 A CN202110865154 A CN 202110865154A CN 113667214 B CN113667214 B CN 113667214B
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- continuous
- fiber
- parts
- riveting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
Landscapes
- 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)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a continuous fiber reinforced polypropylene composite material and a preparation method thereof, wherein the continuous fiber reinforced polypropylene composite material is prepared from 35-37 parts by weight of polypropylene, 61-64 parts by weight of modified continuous glass fiber, 4-5 parts by weight of compatilizer, 0.2-0.3 part by weight of light stabilizer, 0.2-0.3 part by weight of antioxidant and 0.2-0.3 part by weight of lubricant; the preparation method of the modified continuous glass fiber comprises the following steps: spreading 59-61 parts of continuous glass fiber, spraying 2-3 parts of riveted ultrashort glass fiber suspension on the surface of the continuous glass fiber while spreading to enable ultrashort glass fiber to be attached to dispersed fiber bundles, and then baking for 5-10 seconds to obtain the ultra-short glass fiber. The continuous fiber reinforced polypropylene composite material has obviously improved transverse tensile strength, shows ultrahigh transverse mechanical property and expands the application range.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a continuous fiber reinforced polypropylene composite material and a preparation method thereof.
Background
The continuous fiber reinforced thermoplastic composite material is a reinforced thermoplastic composite material with reinforcing fibers arranged in a single direction and the length of the reinforcing fibers is equal to that of the resin sheet, wherein the continuous fibers mainly play a reinforcing role and are the main load carrier, and the resin fixes the spatial positions of the fibers and uniformly transmits stress. Because the reinforcing fiber in the continuous fiber reinforced thermoplastic composite material is unidirectionally and continuously reinforced, the fiber reinforced reinforcing effect can be fully exerted, and the mechanical property of the continuous fiber reinforced thermoplastic composite material is far higher than that of long and short fiber reinforced thermoplastic composite materials. In addition, fiber breakpoints in the continuous fiber reinforced thermoplastic composite material are relatively few, the stress concentration effect can be effectively reduced, and the composite material has better performance. With the rapid development of science and technology, continuous fiber reinforced resin-based composite materials have become widely used engineering materials, and by virtue of the characteristics of high specific strength, high specific modulus, chemical corrosion resistance, fatigue resistance, flexible design and the like, the continuous fiber reinforced resin-based composite materials are widely applied to the industries of aerospace, transportation, building materials, industrial design, sports goods and the like, and become hot spots for development and research of current composite materials.
The longitudinal and transverse tensile strength of polypropylene (PP) is generally 20-30MPa; the longitudinal and transverse tensile strength of long glass fiber reinforced polypropylene (LFTPP) is 100-150MPa, which is 3-5 times of that of pure resin; the conventional unidirectional continuous glass fiber reinforced polypropylene (CFRTPP) has the tensile strength in the fiber direction of 700-800MPa which is 5-8 times that of LFTPP, but has the tensile strength in the vertical fiber direction of only 20-40MPa, so that the strength is very low, the performance cannot be directly applied to some application fields with higher mechanical requirements, and the performance needs to be compensated by a special laying design, so that the difficulty of direct application is greatly increased.
Much research on continuous fiber reinforced polyolefin composite materials is currently carried out, but most of the research focuses on the development of some special functional materials and plates, such as antibacterial (CN 104693594A), special fiber (CN 103289194A), scratch resistance (CN 106995553A), high weather resistance (CN 104530558A), composite plates (CN 202498800U, CN 107877991A), and relatively few researches on transverse tensile strength improvement of unidirectional tapes.
Disclosure of Invention
In view of the above, the present invention provides a continuous fiber reinforced polypropylene composite material and a preparation method thereof, wherein the continuous fiber reinforced polypropylene composite material has excellent transverse mechanical properties due to the transverse riveting reinforcement effect of ultra-short glass fibers between longitudinal continuous fibers.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a continuous fiber reinforced polypropylene composite material which is prepared from the following components in parts by weight:
35-37 Parts of Polypropylene (PP),
61-64 parts of modified continuous glass fiber,
4-5 parts of a compatilizer,
0.2 to 0.3 portion of light stabilizer,
0.2 to 0.3 portion of antioxidant,
0.2-0.3 part of a lubricant;
the preparation method of the modified continuous glass fiber comprises the following steps: spreading 59-61 parts of continuous glass fiber, spraying 2-3 parts of riveted ultrashort glass fiber suspension on the surface of the continuous glass fiber while spreading to enable ultrashort glass fiber to be attached to dispersed fiber bundles, and then baking for 5-10 seconds to obtain the ultra-short glass fiber.
Further, the melt index of the polypropylene under the test conditions of 230 ℃ and 2.16kg is 50-70g/10min.
Further, the compatibilizer is at least one selected from a cyclic acid anhydride graft type compatibilizer and a carboxylic acid graft type compatibilizer.
Further, the light stabilizer is selected from benzotriazole light stabilizers;
the antioxidant is a compound antioxidant, and the compound antioxidant is prepared from the following components in a volume ratio of 1: (1.5-2) hindered phenol antioxidant and phosphite ester antioxidant.
Further, the lubricant is selected from fatty acid amide type lubricants.
Further, the continuous glass fiber is alkali-free glass fiber.
Further, the riveting ultra-short glass fiber suspension is obtained by high-speed dispersion treatment of ultra-short glass fibers and a riveting agent through a coupling agent, and comprises the following steps:
mixing the components in a mass ratio of 0.0001: (0.05-0.055) mixing the coupling agent, the riveting agent and the ultra-short glass fiber of (1-1.5), and dispersing at high speed of 1000-1200r/min for 40-50min to obtain mixed powder;
dispersing the mixed powder in water, and performing ultrasonic treatment for 5-10min to obtain a riveting ultrashort glass fiber suspension, wherein the mass fraction of the ultrashort glass fibers in the riveting ultrashort glass fiber suspension is 1.5-2%.
Further, the coupling agent is selected from at least one of 3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane;
the riveting agent is selected from low-melting-point glass powder, and the particle size of the low-melting-point glass powder is 1-2 mu m;
the length-diameter ratio of the ultrashort glass fiber is (8-15): 1, the diameter is 8-12 μm.
The invention also provides a preparation method of the continuous fiber reinforced polypropylene composite material, which comprises the following steps:
uniformly mixing 35-37 parts by weight of polypropylene, 4-5 parts by weight of compatilizer, 0.2-0.3 part by weight of light stabilizer, 0.2-0.3 part by weight of antioxidant and 0.2-0.3 part by weight of lubricant to obtain premix;
spreading 59-61 parts of continuous glass fiber, spraying 2-3 parts of riveted ultrashort glass fiber suspension on the surface of the continuous glass fiber while spreading, so that the ultrashort glass fiber is attached to the dispersed fiber bundles, and then baking at 400-450 ℃ for 5-10s to obtain modified continuous glass fiber;
and under the anaerobic condition, melting and extruding the premix, mixing the premix with the modified continuous glass fiber, carrying out melt impregnation, cooling and shaping to obtain the continuous fiber reinforced polypropylene composite material.
The temperature of the premix after melting and extrusion is 220-235 ℃;
the temperature of the melt impregnation is 230-240 ℃.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the riveting ultra-short glass fiber turbid liquid is sprayed on the surface of the spread continuous glass fiber and is subjected to high-temperature baking treatment, and the ultra-short glass fiber is riveted and attached to the surface of the continuous glass fiber, so that the original parallel continuous glass fiber without longitudinal interaction is enabled to have the advantages that due to the transverse bridging riveting effect of the ultra-short glass fiber, the transverse tensile strength of the prepared composite material unidirectional tape is obviously improved, and the application range of the polypropylene composite material is greatly expanded.
Furthermore, the riveting ultra-short glass fiber suspension is obtained by high-speed dispersion treatment of ultra-short glass fibers and a riveting agent through a coupling agent, the riveting agent is uniformly dispersed on the ultra-short glass fibers due to the dispersion bridging effect of the coupling agent, the ultra-short glass fibers and the continuous glass fibers are firmly adhered together after the spreading continuous glass fibers are sprayed and heated through the riveting ultra-short glass fiber suspension, and the riveting agent is slightly melted and plays a role of a riveting bolt, so that a firm riveting interface is formed between the ultra-short glass fibers and the continuous glass fibers.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following examples. 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 invention discloses a continuous glass fiber reinforced polypropylene composite material, which is prepared from the following components in parts by weight:
35-37 Parts of Polypropylene (PP),
61-64 parts of modified continuous glass fiber,
4-5 parts of a compatilizer,
0.2 to 0.3 portion of light stabilizer,
0.2 to 0.3 portion of antioxidant,
0.2-0.3 part of a lubricant;
the preparation method of the modified continuous glass fiber comprises the following steps: spreading 59-61 parts of continuous glass fiber, spraying 2-3 parts of riveted ultrashort glass fiber suspension on the surface of the continuous glass fiber while spreading to enable ultrashort glass fiber to be attached to dispersed fiber bundles, and then baking for 5-10s to obtain the ultra-short glass fiber.
According to the invention, the riveting ultra-short glass fiber turbid liquid is sprayed on the surface of the continuous glass fiber and then is subjected to heating treatment, so that the ultra-short glass fiber is attached to and welded on the continuous glass fiber, and the original parallel continuous glass fiber without longitudinal interaction is improved in the transverse tensile strength of the continuous glass fiber reinforced composite material unidirectional tape due to the transverse lapping effect of the ultra-short glass fiber, thereby expanding the application range of the polypropylene composite material. The continuous glass fiber is an outward untwisted yarn, and the linear density of the fiber is 1200Tex and 2400Tex. During the preparation process of the modified continuous glass fiber, the continuous glass fiber is spread by using conventional spreading equipment in the field, and specifically, the continuous glass fiber is guided into the spreading equipment through yarn releasing and guide rollers to disperse fiber bundles so as to realize spreading of the continuous glass fiber; and meanwhile, spraying and riveting ultra-short glass fiber turbid liquid on the surface of the continuous glass fiber at the yarn spreading rear section, so that the ultra-short glass fiber is attached to the fiber bundle while the fiber bundle is dispersed, and finally, baking by adopting a high-temperature furnace to obtain the ultra-short glass fiber yarn.
Further, the polypropylene used as the matrix resin in the present invention is not particularly limited in specific type, and may be adjusted according to the requirement (such as requirement of material property, difference of application field, etc.), and in one or more embodiments of the present invention, the melt index of the polypropylene is 50-70g/10min.
In a further scheme, the compatibilizer is added into the system, and the compatibilizer has strong polar reactive groups, so that the material has high polarity and reactivity, and can greatly increase the bonding force between the matrix resin and the inorganic fiber interface, thereby improving the mechanical strength of the composite material, wherein the type of the compatibilizer is not particularly limited and can be selected according to the matrix resin, and can be at least one of cyclic anhydride grafted compatibilizers and carboxylic acid grafted compatibilizers, and the "cyclic anhydride grafted compatibilizer" referred to herein refers to a maleic anhydride compatibilizer grafted onto polyolefin by maleic anhydride, and the grafting ratio thereof is generally between 0.8 and 1.0%, and specific examples include but are not limited to maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, and the like; the "carboxylic acid graft type compatibilizer" refers to an acrylic type compatibilizer grafted with acrylic acid to polyolefin, and specific examples include, but are not limited to, acrylic graft polypropylene, acrylic graft polyethylene, and the like. In one or more embodiments of the present invention, in order to further exert the effect of the compatibilizer, maleic anhydride-grafted polypropylene or acrylic acid-grafted polypropylene is preferably used.
According to the further scheme, the light stabilizer and the antioxidant are added, so that the prepared sheet has long-term outdoor weather resistance and long-term environmental damp-heat aging resistance. The light stabilizer and the antioxidant in the present invention may be of conventional types in the art, and are not particularly limited, and in one or more embodiments of the present invention, the light stabilizer is selected from benzotriazole light stabilizers, and specific examples include, but are not limited to, UV-P, UV-327 or UV-326, and may be one or a mixture of two or more thereof. In one or more embodiments of the present invention, the antioxidant is a complex antioxidant, and the complex antioxidant is prepared by compounding a hindered phenol antioxidant and a phosphite antioxidant, preferably, the volume ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: (1.5-2), more preferably, the volume ratio is 1:2, wherein, examples that may be specifically mentioned of the hindered phenol type antioxidants include, but are not limited to, antioxidant 1010 or antioxidant 1076; examples of the phosphite antioxidant which may be specifically mentioned include, but are not limited to, antioxidant 168 or antioxidant 626.
In a further aspect, the lubricant is selected from fatty acid amide type lubricants, in one or more embodiments of the present invention, specifically, but not limited to, stearic acid amide, N' -ethylene bis-stearamide, oleic acid amide, or erucic acid amide, and may be one or a mixture of two or more thereof.
In a further aspect, in one or more embodiments of the present invention, the continuous glass fiber is preferably an alkali-free glass fiber, because the alkali-free glass fiber has better mechanical strength and better compatibility with the matrix resin than an alkali or medium alkali glass fiber, and can significantly improve the mechanical properties of the composite material.
In a further aspect, in one or more embodiments of the present invention, the riveting ultra-short glass fiber suspension is obtained by performing high-speed dispersion treatment on ultra-short glass fibers and a riveting agent through a coupling agent, where the "riveting agent" refers to an auxiliary agent with melting and curing capabilities, such as glass powder, and the riveting agent is uniformly dispersed on the ultra-short glass fibers by using a dispersion bridging effect of the coupling agent, and after spraying and heat treatment of the riveting ultra-short glass fiber suspension on the spread continuous glass fibers, the riveting agent is slightly melted, so that the adhesion between the ultra-short glass fibers and the continuous glass fibers is improved, the ultra-short glass fibers and the continuous glass fibers are firmly adhered together, and specifically, in the spraying and heating processes, at a temperature rising stage, due to evaporation of water, the ultra-short glass fibers with the riveting agent on the surfaces thereof are gradually and randomly lapped on the surfaces of the continuous glass fibers, so as to implement physical lapping; and then, along with the completion of the evaporation of water, the surface temperature is further increased, when the temperature exceeds the melting point of the riveting agent, the riveting agent is slightly melted, at the moment, the riveting agent at the lap joint of the ultra-short glass fiber and the continuous glass fiber is slightly welded to two lap joints, and when the subsequent temperature is reduced to be below the melting point of the riveting agent, a firm riveting interface is formed at the lap joint, so that the ultra-short glass fiber is firmly riveted on the surface of the continuous glass fiber, and the transverse tensile strength of the unidirectional tape of the continuous glass fiber reinforced polypropylene composite material is remarkably improved. In some embodiments of the present invention, the preparation of the suspension of riveted ultrashort glass fibers comprises the following steps:
mixing the components in a mass ratio of 0.0001: (0.05-0.055) mixing the coupling agent, the riveting agent and the ultra-short glass fiber of (1-1.5), and dispersing at high speed of 1000-1200r/min for 40-50min to obtain mixed powder;
dispersing the mixed powder in water, and performing ultrasonic treatment for 5-10min to obtain a riveted ultrashort glass fiber suspension, wherein the mass fraction of the ultrashort glass fibers in the riveted ultrashort glass fiber suspension is 1.5-2%.
Further, the coupling agent described in the present invention is not particularly limited and may be a conventional one in the art, and in one or more embodiments of the present invention, the coupling agent is selected from at least one of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane;
in some specific embodiments of the present invention, in consideration of equipment requirements and energy consumption control, the melting point of the riveting agent is preferably 350-520 ℃, for example, the melting point of the low-melting-point glass frit is 350-400 ℃, or the melting point of the medium-melting-point glass frit is 480-520 ℃, and more preferably, in one or more embodiments of the present invention, the riveting agent uses the low-melting-point glass frit, so that the riveting effect of the ultra-short glass fiber is significant, the transverse tensile strength of the composite material is significantly improved, and the energy consumption is low, and in specific operation, the baking temperature is controlled to be higher than the melting point of the riveting agent, preferably, the baking temperature is 5-50 ℃ higher than the melting point of the riveting agent; in the examples of the present invention, commercially available products were used as they were. Generally, the diameter of the continuous glass fiber is 17-20 μm, and in order to realize better lap joint of the ultra-short glass fiber and the continuous fiber and smoothness of processing, in one or more embodiments of the invention, the particle size of the low-melting glass powder is 1-2 μm; the length-diameter ratio of the ultrashort glass fiber is (8-15): 1, the diameter is 8-12 μm.
In a second aspect of the present invention, there is provided a method for preparing a continuous fiber reinforced polypropylene composite according to the first aspect of the present invention, comprising the steps of:
uniformly mixing 35-37 parts by weight of polypropylene, 4-5 parts by weight of compatilizer, 0.2-0.3 part by weight of light stabilizer, 0.2-0.3 part by weight of antioxidant and 0.2-0.3 part by weight of lubricant to obtain a premix, wherein the specific mixing mode, parameters and the like are not particularly limited as long as the uniform mixing of the raw materials can be ensured, and in one or more embodiments of the invention, the raw materials are added into a 65-75 ℃ high-speed mixer to be mixed for 5-10min;
spreading 56-61 parts of continuous glass fiber, spraying 2-3 parts of riveting ultrashort glass fiber suspension on the surface of the continuous glass fiber while spreading, enabling the riveting ultrashort glass fiber to be attached to dispersed fiber bundles, and then baking at 400-450 ℃ for 5-10s to obtain modified continuous glass fiber;
and under the anaerobic condition, melting and extruding the premix, mixing the premix with the modified continuous glass fiber, carrying out melt impregnation, cooling and shaping to obtain the continuous fiber reinforced polypropylene composite material. It can be understood that the melting and extrusion of the premix can be realized by adopting a conventional twin-screw extruder in the field, then the extrusion materials and the modified continuous glass fiber are subjected to melting impregnation, and a traction and winding device is adopted for driving in the process, so that the continuous production is realized. The apparatus of the present invention is not particularly limited and may be selected conventionally in the art.
Further, the melting, extruding and melt-impregnating temperature in the present invention can be adjusted according to the raw material components and the properties of the final material, and is not particularly limited, and in one or more embodiments of the present invention, the temperature of the premix after melting and extruding is 220 to 235 ℃; the temperature of the melt impregnation is 230-240 ℃.
The technical solution of the present invention will be more clearly and completely described below with reference to specific embodiments. In the following examples, "part(s)" and "part(s)" are parts by weight unless otherwise specified. The raw material auxiliaries are all commercially available, but it is understood that the raw material auxiliaries in the following examples are only used for making the technical scheme of the invention clearer, and do not represent that the invention can only use the following raw material auxiliaries, and the specific scope is subject to the claims.
Example 1
The preparation method of the continuous fiber reinforced polypropylene composite material in the embodiment specifically comprises the following steps:
adding 35 parts of polypropylene resin (230 ℃,2.16kg, melt index at 65 g/min), 4 parts of maleic anhydride grafted polypropylene, 0.2 part of UV-327, 0.2 part of a compound antioxidant (1010 168= 1) and 0.2 part of erucamide into a high-speed mixer at 65 ℃ for mixing for 5min to obtain a premix;
ultra-short glass fiber (length-diameter ratio 10:1, diameter 10 μm) and low-melting glass powder (particle diameter 1-2 μm, melting point 350-400 ℃) are stirred and dispersed for 40min at high speed (1200 r/min) by using 3-aminopropyltriethoxysilane, wherein the ratio of 3-aminopropyltriethoxysilane: low-melting glass powder: the mass ratio of the ultra-short glass fiber is 0.0001: 0.05; then adding the treated mixed powder into water, and carrying out ultrasonic treatment at the frequency of 28kHz for 5min to obtain a riveting ultra-short glass fiber suspension, wherein the percentage of ultra-short glass fibers in the riveting suspension is 2%;
59 parts of continuous glass fiber (with the diameter of 17 mu m and the linear density of 1200 Tex) is guided by a yarn releasing and guide roller to enter yarn unfolding equipment for fiber bundle dispersion, 2 parts of riveting ultrashort glass fiber suspension is sprayed on the surface of the rear yarn unfolding section, so that the fiber bundle can be attached to the fiber bundle while being dispersed, and then the fiber bundle is guided by the guide roller to continuously enter a high-temperature furnace with the temperature of 400 ℃ for baking for 5 seconds, so that the ultrashort glass fiber is firmly riveted on the surface of the continuous glass fiber, and then the fiber bundle is guided by another guide roller to enter a dipping die;
under the protection of nitrogen, adding the premix into a main feeding port of a double-screw extruder, performing melt mixing and extrusion on the premix into an impregnation die through the double-screw extruder (the temperature is 220 ℃, the screw rotation speed is 450RPM, and the vacuum degree is-0.04 MPa) to perform shunting, performing melt impregnation (the impregnation temperature is 230 ℃) on the fully impregnated continuous fiber bundle and the continuous fiber after riveting the ultrashort glass fiber, performing cooling shaping on the fully impregnated continuous fiber bundle through a cooling shaping device, and performing continuous production under the driving of a traction and winding device to prepare the continuous fiber reinforced polypropylene composite material.
Example 2
The preparation method of the continuous fiber reinforced polypropylene composite material in the embodiment specifically comprises the following steps:
adding 37 parts of polypropylene resin (230 ℃,2.16kg, melt index at 65 g/min), 5 parts of maleic anhydride grafted polypropylene, 0.3 part of UV-327, 0.3 part of a compound antioxidant (1010 168= 1) and 0.3 part of erucamide into a high-speed mixer at 75 ℃ for mixing for 10min to obtain a premix;
obtaining a riveting ultrashort glass fiber suspension with an ultrashort glass fiber accounting for 2% in the same manner as in the embodiment 1;
61 parts of continuous glass fiber (diameter is 17 mu m, linear density is 1200 Tex) is guided to enter a yarn spreading device through yarn releasing and guide rollers to disperse fiber tows, 3 parts of riveting ultrashort glass fiber suspension is sprayed on the surface of the yarn spreading rear section, so that the fiber tows can be attached to the fiber tows in a dispersing and riveting ultrashort glass fiber, then the fiber tows are guided to continuously enter a high-temperature furnace with the temperature of 450 ℃ through the guide rollers to be baked for 10s, the ultrashort glass fiber is firmly riveted on the surface of the continuous glass fiber, and then the fiber tows are guided to enter a dipping die through another guide roller;
under the protection of nitrogen, adding the premix into a main feeding port of a double-screw extruder, performing melt mixing and extrusion on the premix into an impregnation die through the double-screw extruder (the temperature is 235 ℃, the screw rotation speed is 500RPM, and the vacuum degree is-0.1 MPa) to perform shunting, performing melt impregnation (the impregnation temperature is 240 ℃) on the fully impregnated continuous fiber bundle and continuous fibers after riveting the ultrashort glass fibers, performing cooling shaping on the fully impregnated continuous fiber bundle through a cooling shaping device, and performing continuous production under the driving of a traction and winding device to prepare the continuous fiber reinforced polypropylene composite material.
Comparative example 1
The preparation method of the continuous fiber reinforced polypropylene composite material in the embodiment specifically comprises the following steps:
adding 35 parts of polypropylene resin (230 ℃,2.16kg, melt index at 65 g/min), 4 parts of maleic anhydride grafted polypropylene, 0.2 part of UV-327, 0.2 part of a compound antioxidant (1010 168= 1) and 0.2 part of erucamide into a high-speed mixer at 65 ℃ for mixing for 5min to obtain a premix;
59 parts of continuous glass fiber (diameter is 17 mu m, linear density is 1200 Tex) is guided by a yarn releasing and guide roller to enter a yarn spreading device for fiber strand dispersion, then is guided by the guide roller to continuously enter a high-temperature furnace with the temperature of 400 ℃ for baking for 5s, and then is guided by another guide roller to enter an impregnation die;
under the protection of nitrogen, adding the premix into a main feeding port of a double-screw extruder, melting, mixing and extruding the premix into an impregnation die through the double-screw extruder (the temperature is 220 ℃, the screw rotation speed is 450RPM, and the vacuum degree is-0.04 MPa) to perform shunting and melt impregnation (the impregnation temperature is 230 ℃) with continuous glass fibers, cooling and shaping the fully impregnated continuous fiber bundle through a cooling and shaping device, and performing continuous production under the driving of a traction and winding device to prepare the continuous fiber reinforced polypropylene composite material.
Comparative example 2
This comparative example uses the same embodiment as example 1 except that: the method for attaching the ultrashort glass fiber to the continuous glass fiber comprises the steps of guiding the continuous glass fiber to enter yarn spreading equipment for fiber bundle dispersion through yarn releasing (the diameter is 17 mu m, and the linear density is 1200 Tex) and a guide roller, spraying and riveting ultrashort glass fiber suspension on the surface of the rear yarn spreading section to enable micron low-melting-point glass powder to be attached to the fiber bundle while dispersing the fiber bundle, then guiding the fiber bundle to continuously enter a high-temperature furnace at 100 ℃ through the guide roller for baking for 5s, and then guiding the fiber bundle to enter a dipping die through another guide roller. The rest of the procedure was the same as in example 1.
Comparative example 3
This comparative example uses the same embodiment as example 1 except that: (1) adopting medium-melting-point glass powder (the particle size is 1-2 μm, the melting point is 480-520 ℃) in the riveting ultrashort glass fiber suspension; (2) in the step of riveting the ultra-short glass fiber to the continuous glass fiber, the high temperature furnace temperature is set to 400 ℃.
The other compositions and steps were the same as in example 1.
Test example
The continuous fiber reinforced polypropylene composites prepared in examples 1-2 and comparative examples 1-3 were subjected to a transverse tensile strength (perpendicular to the glass fiber direction) test, respectively, and the results are shown in Table 1.
TABLE 1 Performance test results for continuous fiber reinforced Polypropylene composites
| Typical Properties | Test method | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Transverse tensile strength/MPa | ASTM D3039 | 60 | 71 | 25 | 28 | 27 |
As can be seen from the test results in table 1, the polypropylene composites obtained in examples 1 and 2 exhibited ultra high transverse tensile strength. In the embodiment 1, the tensile strength is higher than that in the comparison 1, which shows that the riveting effect of the low-melting-point glass powder on the continuous fibers is obvious, so that the transverse tensile strength of the composite material is obviously improved; the tensile strength of the comparative example 2 is not much different from that of the comparative example 3, and the tensile strength is larger than that of the comparative example 1, but the tensile strength of the three is far lower than that of the transverse tensile strength of the comparative example 1, which shows that under the condition that the low-melting-point glass powder is not fused and adhered, although weak coupling action exists between the ultrashort glass fiber and the continuous glass fiber, the transverse high tensile strength is far smaller than that of the fusion and adhesion, so that the transverse high tensile strength in the example 1 is derived from the fusion riveting and adhesion action of the low-melting-point glass powder on the ultrashort glass fiber and the continuous glass fiber.
In order to further embody the technical scheme of the invention, the invention also carries out the following parallel embodiments:
example 3
The preparation method of the continuous fiber reinforced polypropylene composite material in the embodiment specifically comprises the following steps:
adding 36 parts of polypropylene resin (230 ℃,2.16kg, melt index is 50 g/min), 4 parts of acrylic grafted polypropylene, 0.2 part of UV-P, 0.2 part of compound antioxidant (1010 168= 1.5) and 0.2 part of oleamide into a high-speed mixer at the temperature of 65 ℃ for mixing for 5min to obtain a premix;
ultra-short glass fiber (length-diameter ratio 8:1, diameter 8 μm) and low-melting glass powder (particle diameter 1-2 μm) were stirred and dispersed at high speed (1000 r/min) for 45min using 3-glycidoxypropyltrimethoxysilane, wherein 3-glycidoxypropyltrimethoxysilane: low-melting glass powder: the mass ratio of the ultra-short glass fiber is 0.0001:0.055:1; then adding the treated mixed powder into water, and carrying out ultrasonic treatment at the frequency of 28kHz for 5min to obtain a riveted ultrashort glass fiber suspension, wherein the ultrashort glass fiber accounts for 1.5%;
60 parts of continuous glass fiber (with the diameter of 17 mu m and the linear density of 2400 Tex) is guided by a yarn releasing and guide roller to enter a yarn unfolding device for fiber strand dispersion, 2 parts of riveting ultrashort glass fiber suspension is sprayed on the surface of the rear yarn unfolding section, so that the fiber strand can be attached to the fiber strand while being dispersed, then the fiber strand is guided by the guide roller to continuously enter a high-temperature furnace with the temperature of 420 ℃ for baking for 6s, so that the ultrashort glass fiber is firmly riveted on the surface of the continuous glass fiber, and then the fiber strand is guided by another guide roller to enter a dipping die;
under the protection of nitrogen, adding the premix into a main feeding port of a double-screw extruder, carrying out melt mixing extrusion on the premix and continuous fibers riveted with the ultra-short glass fibers in an impregnation die through the double-screw extruder (the temperature is 230 ℃, the screw rotating speed is 450RPM, and the vacuum degree is-0.04 MPa) to carry out shunting and melt impregnation (the impregnation temperature is 235 ℃), cooling and shaping the fully impregnated continuous fiber bundles through a cooling and shaping device, and carrying out continuous production under the driving of a traction and winding device to obtain the continuous fiber reinforced polypropylene composite material.
Example 4
The preparation method of the continuous fiber reinforced polypropylene composite material in the embodiment specifically comprises the following steps:
adding 36 parts of polypropylene resin (230 ℃,2.16kg, melt index at 70 g/min), 5 parts of acrylic acid grafted polypropylene, 0.3 part of UV-326, 0.3 part of compound antioxidant (1010, 168=1.5) and 0.2 part of stearic acid amide into a high-speed mixer at 65 ℃ for mixing for 10min to obtain a premix;
ultra-short glass fiber (length-diameter ratio 15:1, diameter: 12 μm) and low-melting glass powder (particle diameter: 1-2 μm) were subjected to high-speed (1100 r/min) stirring dispersion treatment using 3-glycidoxypropyltrimethoxysilane for 50min, wherein the ratio of 3-glycidoxypropyltrimethoxysilane: low-melting glass powder: the mass ratio of the ultra-short glass fiber is 0.0001:0.05:1.5; then adding the treated mixed powder into water, and carrying out ultrasonic treatment at the frequency of 28kHz for 10min to obtain a riveted ultrashort glass fiber suspension, wherein the ultrashort glass fiber accounts for 1.5%;
60 parts of continuous glass fiber (with the diameter of 17 mu m and the linear density of 2400 Tex) is guided by a yarn releasing and guide roller to enter a yarn unfolding device for fiber strand dispersion, 3 parts of riveting ultrashort glass fiber suspension is sprayed on the surface of the rear yarn unfolding section, so that the fiber strand can be attached to the fiber strand while being dispersed, then the fiber strand is guided by the guide roller to continuously enter a high-temperature furnace with the temperature of 420 ℃ for baking for 10s, so that the ultrashort glass fiber is firmly riveted on the surface of the continuous glass fiber, and then the fiber strand is guided by another guide roller to enter a dipping die;
under the protection of nitrogen, adding the premix into a main feeding port of a double-screw extruder, performing melt mixing and extrusion on the premix into an impregnation die through the double-screw extruder (the temperature is 235 ℃, the screw rotation speed is 450RPM, and the vacuum degree is-0.04 MPa) to perform shunting, performing melt impregnation (the impregnation temperature is 240 ℃) on the fully impregnated continuous fiber bundle and continuous fibers after riveting the ultrashort glass fibers, performing cooling shaping on the fully impregnated continuous fiber bundle through a cooling shaping device, and performing continuous production under the driving of a traction and winding device to prepare the continuous fiber reinforced polypropylene composite material.
Example 5
The present example employs the same embodiment as example 1, except that: (1) adopting medium-melting-point glass powder (with the particle size of 1-2 mu m and the melting point of 480-520 ℃) in the riveting ultra-short glass fiber suspension; (2) in the step of riveting the ultra-short glass fiber to the continuous glass fiber, the high temperature furnace temperature was set to 520 ℃.
The continuous fiber reinforced polypropylene composite materials prepared in the examples 3-5 are tested in the same test mode as the examples 1-2, and the transverse tensile strength in the examples 3-5 is 55-65MPa, which shows that the transverse tensile strength of the continuous fiber reinforced polypropylene composite materials can be remarkably improved and the transverse tensile resistance can be remarkably improved by riveting the ultra-short glass fibers on the continuous glass fibers.
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 (8)
1. The continuous fiber reinforced polypropylene composite material is characterized by being prepared from the following components in parts by weight:
35-37 Parts of Polypropylene (PP),
61-64 parts of modified continuous glass fiber,
4-5 parts of a compatilizer,
0.2 to 0.3 portion of light stabilizer,
0.2 to 0.3 portion of antioxidant,
0.2-0.3 part of lubricant;
the preparation method of the modified continuous glass fiber comprises the following steps: spreading 59-61 parts of continuous glass fiber, spraying 2-3 parts of riveted ultrashort glass fiber suspension on the surface of the continuous glass fiber while spreading, attaching the ultrashort glass fiber to the dispersed fiber bundles, and baking at 400-450 ℃ for 5-10s to obtain the ultra-short glass fiber;
the riveting ultra-short glass fiber suspension is obtained by high-speed dispersion treatment of ultra-short glass fibers and a riveting agent through a coupling agent, and comprises the following steps:
mixing the components in a mass ratio of 0.0001: (0.05-0.055) mixing the coupling agent, the riveting agent and the ultra-short glass fiber of (1-1.5), and dispersing at high speed of 1000-1200r/min for 40-50min to obtain mixed powder;
dispersing the mixed powder in water, and performing ultrasonic treatment for 5-10min to obtain a riveting ultrashort glass fiber suspension, wherein the mass fraction of the ultrashort glass fibers in the riveting ultrashort glass fiber suspension is 1.5-2%;
the riveting agent is low-melting-point glass powder with a melting point of 350-400 ℃, and the particle size of the low-melting-point glass powder is 1-2 mu m; the length-diameter ratio of the ultrashort glass fiber is (8-15): 1, the diameter is 8-12 μm.
2. The continuous fiber reinforced polypropylene composite of claim 1, wherein the polypropylene has a melt index of 50 to 70g/10min at 230 ℃ under a 2.16kg test.
3. The continuous fiber reinforced polypropylene composite of claim 1, wherein the compatibilizer is at least one selected from the group consisting of a cyclic anhydride grafted compatibilizer, and a carboxylic acid grafted compatibilizer.
4. The continuous fiber reinforced polypropylene composite of claim 1, wherein the lubricant is selected from fatty acid amide type lubricants.
5. The continuous fiber reinforced polypropylene composite of claim 1, wherein the continuous glass fiber is an alkali-free glass fiber.
6. The continuous fiber reinforced polypropylene composite of claim 1, wherein the coupling agent is at least one selected from the group consisting of 3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.
7. The process for preparing a continuous fiber reinforced polypropylene composite according to any one of claims 1 to 6, comprising the steps of:
uniformly mixing 35-37 parts by weight of polypropylene, 4-5 parts by weight of compatilizer, 0.2-0.3 part by weight of light stabilizer, 0.2-0.3 part by weight of antioxidant and 0.2-0.3 part by weight of lubricant to obtain premix;
spreading 59-61 parts of continuous glass fiber, spraying 2-3 parts of riveted ultrashort glass fiber suspension on the surface of the continuous glass fiber while spreading, so that the ultrashort glass fiber is attached to the dispersed fiber bundles, and then baking at 400-450 ℃ for 5-10s to obtain modified continuous glass fiber;
and under the anaerobic condition, melting and extruding the premix, mixing the premix with the modified continuous glass fiber, carrying out melt impregnation, cooling and shaping to obtain the continuous fiber reinforced polypropylene composite material.
8. The method of claim 7, wherein the temperature of the molten and extruded premix is 220 to 235 ℃;
the temperature of the melt impregnation is 230-240 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110865154.7A CN113667214B (en) | 2021-07-29 | 2021-07-29 | Continuous fiber reinforced polypropylene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110865154.7A CN113667214B (en) | 2021-07-29 | 2021-07-29 | Continuous fiber reinforced polypropylene composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113667214A CN113667214A (en) | 2021-11-19 |
| CN113667214B true CN113667214B (en) | 2022-12-02 |
Family
ID=78540748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110865154.7A Active CN113667214B (en) | 2021-07-29 | 2021-07-29 | Continuous fiber reinforced polypropylene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113667214B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316313B (en) * | 2021-12-21 | 2023-03-10 | 南京工业大学 | Long and short glass fiber hybrid reinforced polypropylene base station antenna outer cover composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8414634D0 (en) * | 1983-06-08 | 1984-07-11 | Mitsubishi Petrochemical Co | Glass fiber reinforced resin compositions |
| 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 |
| CN111534082A (en) * | 2020-06-12 | 2020-08-14 | 江苏省建筑科学研究院有限公司 | Transverse reinforced glass fiber reinforced polyurethane pultrusion profile and preparation method thereof |
-
2021
- 2021-07-29 CN CN202110865154.7A patent/CN113667214B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8414634D0 (en) * | 1983-06-08 | 1984-07-11 | Mitsubishi Petrochemical Co | Glass fiber reinforced resin compositions |
| 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 |
| CN111534082A (en) * | 2020-06-12 | 2020-08-14 | 江苏省建筑科学研究院有限公司 | Transverse reinforced glass fiber reinforced polyurethane pultrusion profile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113667214A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5021066B2 (en) | Method for producing heat-treated carbon long fiber reinforced resin pellets | |
| WO2022252661A1 (en) | Continuous long fiber-reinforced thermoplastic composite board, and preparation method therefor and use thereof | |
| CN113667214B (en) | Continuous fiber reinforced polypropylene composite material and preparation method thereof | |
| US9303131B2 (en) | Premolding article from thermoset and thermoplastic polymer dispersions | |
| KR20170010308A (en) | Method for impregnating natural fibres with a polymer in aqueous dispersion and use of said fibres in composite materials | |
| KR20170104369A (en) | Continuous device for impregnating, in a single step, strands or ribbons of natural fibres, in particular linen | |
| CN102367313A (en) | Glass fiber reinforced polypropylene composite material and preparation method thereof | |
| US20240052115A1 (en) | Long-carbon-chain polyamide resin composition and continuous fiber reinforced long-carbon-chain polyamide composite material | |
| CN106009333A (en) | Carbon fiber reinforced polypropylene composite and application | |
| CN104910615B (en) | A kind of high-strength nylon/glass fiber composite material and its manufacturing equipment and manufacture method | |
| CN111073244B (en) | Polycarbonate composition and preparation method thereof | |
| JP2007112041A (en) | Carbon filament reinforced resin molded article and its manufacturing method | |
| CN104231604A (en) | Modified carbon fiber-reinforced composite material and preparation method thereof | |
| CN113789008B (en) | Superstrong continuous fiber reinforced polyolefin composite material and preparation method thereof | |
| CN103540124A (en) | Wear-resistant thermoplastic resin composite material and preparation method thereof | |
| TW201522498A (en) | Continuous fiber thermoplastic composites | |
| JP6566819B2 (en) | Propylene resin fiber bundle | |
| CN103571183A (en) | Continuous glass fiber reinforced nylon 6 prepreg tape and preparation method thereof | |
| WO2022227751A1 (en) | Polyamide 56 resin composition and continuous fiber reinforced polyamide 56 composite material | |
| CN109676908B (en) | Method for preparing pipe by winding and forming short fiber reinforced thermoplastic polymer | |
| CN104250420A (en) | Long-glass-fiber reinforced polypropylene product and preparation method thereof | |
| CN110344252B (en) | Carbon fiber surface treatment method for reinforcing thermoplastic resin | |
| CN111574731A (en) | Preparation method of modified carbon fiber reinforced nylon particles | |
| CN110699960A (en) | Sizing agent for thermoplastic resin reinforced fibers | |
| CN114213751B (en) | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |