CN114149651A - Long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance and preparation process thereof - Google Patents
Long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance and preparation process thereof Download PDFInfo
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- CN114149651A CN114149651A CN202111620112.3A CN202111620112A CN114149651A CN 114149651 A CN114149651 A CN 114149651A CN 202111620112 A CN202111620112 A CN 202111620112A CN 114149651 A CN114149651 A CN 114149651A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 149
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000000835 fiber Substances 0.000 title claims abstract description 54
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 49
- -1 polypropylene Polymers 0.000 title claims abstract description 48
- 238000007667 floating Methods 0.000 title claims abstract description 39
- 238000003878 thermal aging Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 24
- 238000007598 dipping method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 238000001764 infiltration Methods 0.000 description 10
- 230000008595 infiltration Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 239000000243 solution Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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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
- C08J2323/14—Copolymers of propene
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance, which comprises the following preparation raw materials: polypropylene PP: 50-70 parts of glass fiber: 30-50 parts of a functional compatilizer: 3-15 parts of a lubricant: 0.2-1 part of antioxidant: 0.7-1.5 parts; the glass fiber is pretreated alkali-free continuous glass fiber with the diameter of 11-20 mu m; in the preparation process, continuous glass fibers are scattered through a glass fiber scattering device, wherein the rotating speed of the glass fiber scattering device is 18-35 rpm; and (3) after the glass fibers are scattered, baking at high temperature, then entering a dipping die head, and dipping and coating the glass fibers and the extruded molten PP mixture in the dipping die head. The long glass fiber reinforced PP material with low odor, low floating fiber and thermal aging resistance prepared by the invention meets the use requirements of accessory plastic parts of automobile engines. The PP reinforced material is not easy to age under long-term high-temperature conditions, has small change of toughness and strength performance, and is suitable for manufacturing accessory parts of automobile engines.
Description
Technical Field
The invention belongs to the field of polypropylene PP (polypropylene) reinforced materials, and particularly relates to a long glass fiber reinforced PP material with low odor, low floating fiber and thermal aging resistance and a preparation process thereof.
Background
In general, the reinforcing effect of polypropylene PP resins is achieved by adding glass fibers or mineral powder. The long glass fiber reinforced PP has the advantages that the glass fibers are parallel to the axial direction of the aggregate, the length of the long glass fibers is longer, and the effects of toughening and reinforcing can be achieved in the PP. After the PP resin is reinforced by the glass fiber, the strength of the PP resin can reach more than several times of the original strength, and the higher the strength is, the higher the heat resistance is, and the more stable the size is. Therefore, the PP reinforced material can be used as an important material for replacing steel by plastic and is widely applied to various mechanical parts. With the continuous development of light weight of automobiles, the long glass fiber reinforced PP material is gradually applied to auxiliary parts around the automobile engine and can replace a part of metal parts, thereby achieving the effects of reducing weight and improving economic benefit. However, because the ambient temperature of the engine is high, the PP is easy to age under a long-term high-temperature condition, so that the toughness and the strength performance of the material are reduced, and the use requirements of accessory materials around the engine are difficult to meet. With the increase of the content of the glass fiber, the surface of the plastic part is more likely to have floating fiber, and the appearance of the plastic part is affected.
CN201510968817.2 discloses an alkali-free glass fiber reinforced modified polypropylene composite material and a preparation method thereof, wherein the alkali-free glass fiber reinforced modified polypropylene composite material comprises the following raw materials in parts by mass: 45-55 parts of homopolymerized PP resin; 28-32 parts of alkali-free glass fiber; 13-17 parts of talcum powder; 4-6 parts of a compatilizer; 0.5-2 parts of antioxidant and 0.5-2 parts of anti-floating fiber agent; 0.5-2 parts of a lubricant. According to the invention, part of superfine talcum powder is added into the PP glass fiber reinforced material, and talcum powder with a length-diameter ratio smaller than that of glass fiber is used, so that a large-particle lubricating and dispersing effect can be achieved in a formula mixture, and alkali-free glass fiber with a large length-diameter ratio can be well and uniformly dispersed in the material. However, talc powder has a general dispersion assisting effect on long fibers, and in the above invention, fibers are directly mixed with other raw materials and melt-extruded, which causes severe abrasion on long fibers.
CN201610324096.6 discloses a low-floating-fiber glass fiber reinforced polypropylene material and a preparation method thereof, wherein the low-floating-fiber glass fiber reinforced polypropylene material is prepared from the following raw materials in parts by weight: 100 parts of polypropylene resin; 15-30 parts of high-melt-strength polypropylene; 10-50 parts of glass fiber; 1-3 parts of a compatilizer; 5-15 parts of an ethylene-propylene block copolymer; 1-2 parts of other auxiliary agents. The preparation method adopts screw extrusion processing, and the screw combination design principle is as follows: the first zone to the second zone only consist of conveying elements, the third zone to the seventh zone all contain shearing elements, the eighth zone to the tenth zone only consist of conveying elements, and the extrusion temperature is 165-230 ℃. According to the glass fiber reinforced PP, through the design of screw combination in the screw extrusion process, the high melt strength polypropylene wraps glass fibers, but the fibers and other raw materials are directly mixed, melted and extruded, so that long fibers are abraded to a certain extent, and the strength of the material is reduced.
Disclosure of Invention
The invention aims to provide a long glass fiber reinforced PP material with low odor, low floating fiber and heat aging resistance.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance is prepared from the following raw materials in parts by weight:
polypropylene PP: 50 to 70 parts of
Long glass fibers: 30 to 50 portions of
Functional compatilizer: 3 to 15 portions of
Lubricant: 0.2 to 1 portion
Antioxidant: 0.7-1.5 parts;
the glass fiber is alkali-free continuous glass fiber which is pretreated, and the diameter of each monofilament is 11-20 mu m. The total wrap angle of the continuous glass fibers is 270 degrees, and the tension of the glass fibers is 25-30N. Generally, when the total wrap angle of the fiber bundle is 270 ° and the fiber tension is about 25N, the glass fibers can be well dispersed, and the long fibers cannot be damaged, so that the reinforcing effect of the fibers is not affected; too high a total wrap angle and fiber tension tend to exacerbate the degree of fiber abrasion, severely affecting its reinforcement.
In the preparation process, continuous glass fibers are scattered by a glass fiber scattering device, wherein the rotating speed of the glass fiber scattering device is 18-35 rpm; baking the glass fibers through a high-temperature cabinet after the glass fibers are scattered, enabling the glass fibers to enter a dipping die head, and dipping and coating the glass fibers and the extruded molten PP mixture in the dipping die head; and the continuous glass fiber enters the impregnation die head and is drawn by a drawing machine, and the drawing speed is 350-600 rpm.
In the invention, the long glass fibers are scattered by the glass fiber scattering device, the continuous and hard glass fiber bundles are changed into soft and fine glass fiber monofilaments, and the glass fibers are heated uniformly during high-temperature baking, so that the glass fibers are favorably dispersed, impregnated and coated in the extruded molten PP in the infiltration die head. In addition, the continuous glass fiber cluster is broken into soft filaments, so that the strength of the composite material can be improved, the fiber floating is prevented, and the composite material is ageing-resistant. If the scattering degree is not complete, the original glass fiber bundle is larger and harder, and is difficult to be completely infiltrated and coated by PP, the finally manufactured part can have serious fiber floating. The continuous glass fiber enters the infiltration die head and is powered by a tractor, and the speed of the tractor is 350-600 rpm. The slower the traction speed is, the longer the continuous glass fiber stays in the infiltration die head, the better the infiltration and coating effects in the die head are, the material strength can be increased, and the floating fiber can be reduced. The glass fiber scattering device has the advantages that the rotating speed of the glass fiber scattering device is 18-35rpm, each glass fiber bundle consists of thousands of strands of monofilaments, when the glass fiber bundle is baked in a high-temperature cabinet, a bundling agent in the glass fibers is quickly removed, and when the glass fiber bundle passes through the rotating scattering device blades, the glass fiber bundle is scattered through mechanical movement, the glass fiber bundle is scattered into a soft monofilament state, the impregnation coating effect is effectively improved, the strength of materials is increased, and the floating fibers are reduced.
According to the molecular structure characteristics and the similar compatibility principle, the compatibility is improved by adopting the functional compatilizer which is both PP-philic and glass fiber-philic. In the invention, preferably, the functional compatilizer is maleic anhydride grafted polypropylene, wherein the grafting rate of the maleic anhydride grafted polypropylene is more than or equal to 1%, and the mass fraction of maleic anhydride is 2%. The maleic anhydride grafted polypropylene introduces polar side chain groups on a nonpolar molecular main chain, has amphipathy similar to a surfactant, can be used as a bridge for enhancing the compatibility and compounding of polar materials and nonpolar materials (forming micelles similarly), improves the infiltration, winding and coating effects between PP materials and glass fibers, enhances the strength of the materials, and reduces the surface floating fibers of injection molding parts. Meanwhile, the preferable maleic anhydride monomer has good grafting activity, high maleic anhydride grafting rate and low monomer residue, so that the odor is low.
In the present invention, preferably, the pretreatment mode of the glass fiber is: a. soaking the continuous glass fiber into an acrylic acid or acrylate solution for 8-12 h at the temperature of 30-65 ℃; b. and naturally airing the soaked continuous glass fiber, and drying in a drying oven at 150 ℃ for later use. By the pretreatment method, carboxyl is grafted to the glass fiber, so that the bonding strength of the glass fiber and a matrix is improved, and better comprehensive mechanical properties are obtained. Preferably, the glass fiber diameter is 16 μm.
In the invention, the PP is a specific type of block copolymer PP or a mixture of different types of block copolymer PP, and the melt index is more than 70g/10 min. Further preferably, the PP is a block copolymer PP with a specific model and the melt index is 100g/10 min. Polypropylene PP is divided into homo-polypropylene (PP-H), block copolymer polypropylene (PP-B) and random copolymer polypropylene (PP-R), wherein the block copolymer PP-B has the properties of high strength and impact resistance.
In the invention, preferably, the antioxidant is one or a mixture of several of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant AO-412S, and preferably the mixture of antioxidant 1010, antioxidant 168 and antioxidant AO-412S in a weight ratio of 2:1: 4. Has the characteristics of long-term high temperature resistance, excellent heat resistance and low volatility.
In the invention, preferably, the lubricant is one or a mixture of more of lubricant EBS, lubricant PETS and silicone powder. The preferred lubricant is silicone powder. The lubricant has the functions of improving the lubricity in the processing process, reducing the friction between a molten body and the surface of a machine part, reducing the interface adhesion performance, improving the flowability, and playing the roles of a melting promoter, an anti-adhesion and antistatic agent, a slipping agent and the like.
In the invention, preferably, the low-odor, low-floating-fiber and heat-aging-resistant long glass fiber reinforced polypropylene material is prepared from the following raw materials in parts by weight:
the proportion of the raw materials, the high glass fiber content can obviously improve the mechanical strength, heat resistance and dimensional stability of the PP, simultaneously the dosage of the compatilizer is improved, the dosage of other components is controlled, the smell is low, and the floating fiber is reduced.
The invention also provides a preparation method of the long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance, which comprises the following steps:
s1, respectively weighing PP, a functional compatilizer, a lubricant and an antioxidant in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
s2, adding the uniformly mixed material in the step S1 into a double-screw extruder for plasticizing;
and S3, pressing the PP mixture plasticized after the S2 into a dipping die head through which continuous glass fibers pass by using a screw extruder, and preparing the PP reinforced material with the length of 10-14mm through traction, cooling and grain cutting treatment.
The use conditions of the twin-screw extruder are as follows: the extrusion temperature and the temperature of the dipping die head are 220-240 ℃, and the rotating speed of the extruder host is 300-420 rpm.
The viscosity of PP is higher when melting, and the impregnation of long glass fiber is more difficult, and how to improve the impregnation effect of long glass fiber and molten PP, the long glass fiber and molten PP are in full contact and have good compatibility effect, which is a difficult problem in processing and production. The preparation process improves the compatibility of the compatilizer and the impregnation extrusion through the selection of the compatilizer and the setting of the impregnation extrusion process conditions, and simultaneously has good impregnation and coating effects.
Compared with the prior art, the invention has the beneficial effects that:
1. the long glass fiber reinforced PP material with low odor, low floating fiber and thermal aging resistance prepared by the invention meets the use requirements of accessory plastic parts of automobile engines. The PP reinforced material is not easy to age under long-term high-temperature conditions, has small change of toughness and strength performance, and is suitable for manufacturing accessory parts of automobile engines.
2. In the invention, the continuous glass fiber is scattered by the glass fiber scattering device, the long glass fiber bundles are scattered into fine monofilaments, and the fine monofilaments are heated uniformly during high-temperature baking, so that the continuous glass fiber bundles are impregnated and coated with the extruded molten PP in the infiltration die head, the strength of the material is improved, and the floating of the fiber is prevented. The continuous glass fiber enters the infiltration die head and is powered by a tractor, and the speed of the tractor is 350-600 rpm. The slower the traction speed is, the longer the residence time of the continuous glass fiber in the infiltration die head is, the better the infiltration effect in the die head is, the material strength is increased, and the fiber floating is reduced.
3. The functional compatilizer adopted by the invention is maleic anhydride grafted polypropylene, the grafting rate of the maleic anhydride is more than or equal to 1%, and the mass fraction of the maleic anhydride is 2%. The maleic anhydride grafted polypropylene obviously improves the infiltration, winding and coating effects between the PP material and the glass fiber, improves the strength and reduces the surface floating fiber. Meanwhile, the preferable maleic anhydride monomer has good grafting activity, high maleic anhydride grafting rate, low monomer residue and low odor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, but the scope of the present invention is not limited to the embodiments.
In the following embodiments, the raw materials are commercially available unless otherwise specified.
Wherein, the PP is block copolymer PP-B with a melt index of 100g/10 min.
The diameter of the adopted glass fiber is 16 μm, and the pretreatment steps are as follows: a. soaking continuous glass fiber in acrylic acid or acrylate solution for 10h at 50 ℃; b. and naturally airing the soaked continuous glass fiber, and drying in a drying oven at 150 ℃.
The functional compatilizer is maleic anhydride grafted polypropylene, wherein the grafting rate of the maleic anhydride is more than or equal to 1 percent, and the mass fraction of the maleic anhydride is 2 percent.
The lubricant is selected from silicone powder.
The antioxidant is a mixture of an antioxidant 1010, an antioxidant 168 and an antioxidant AO-412S in a weight ratio of 2:1: 4.
Example 1
The long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance is prepared from the following raw materials:
polypropylene PP56Kg
40Kg of glass fiber
4Kg of functional compatilizer
0.5Kg of lubricant
1.2Kg of antioxidant.
The preparation method of the long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance comprises the following steps:
s1, respectively weighing PP, a functional compatilizer, a lubricant and an antioxidant in proportion, and stirring in a high-speed stirrer for 8 minutes;
s2, adding the uniformly mixed material in the step S1 into a double-screw extruder for plasticizing;
s3, scattering the glass fibers by a glass fiber scattering device, wherein the rotating speed of the glass fiber scattering device is 28 rpm; after being scattered, the mixture enters an impregnation die head after being baked in a high-temperature cabinet (90-110 ℃, the linear speed is 1.0-1.5m/s, and the heating time is about 1 s); the glass fiber enters the dipping die head and is drawn by a drawing machine, and the drawing speed is 450 rpm;
and S4, pressing the PP mixture plasticized after the S2 into a dipping die head through which glass fibers pass by using a screw extruder, and carrying out traction, cooling and grain cutting treatment to prepare the PP reinforced material with the length of 10-14mm, wherein the extrusion temperature and the temperature of the dipping die head are 220-240 ℃, and the rotating speed of a main machine of the extruder is 420 rpm.
The PP composite of this example was tested using ISO standards and the results are shown in table 1 below.
Table 1 test results of example 1
Example 2
The long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance is prepared from the following raw materials:
polypropylene PP66Kg
Glass fiber 30Kg
4Kg of functional compatilizer
0.5Kg of lubricant
1.2Kg of antioxidant.
The preparation method of the long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance comprises the following steps:
s1, respectively weighing PP, a functional compatilizer, a lubricant and an antioxidant in proportion, and stirring in a high-speed stirrer for 8 minutes;
s2, adding the uniformly mixed material in the step S1 into a double-screw extruder for plasticizing;
s3, scattering the glass fibers by a glass fiber scattering device, wherein the rotating speed of the glass fiber scattering device is 28 rpm; baking in a high-temperature cabinet (90-110 ℃, linear speed of 1.0-1.5m/s and heating time of about 1 s) after scattering, and then feeding into an impregnation die head; the glass fiber enters the impregnation die head and is drawn by a drawing machine, and the drawing speed is 500 rpm;
and S4, pressing the PP mixture plasticized after the S2 into a dipping die head through which glass fibers pass by using a screw extruder, and carrying out traction, cooling and grain cutting treatment to prepare the PP reinforced material with the length of 10-14mm, wherein the extrusion temperature and the temperature of the dipping die head are 220-240 ℃, and the rotating speed of a main machine of the extruder is 420 rpm.
The PP composite of this example was tested using ISO standards and the results are shown in table 2 below.
Table 2 test results of example 2
Example 3
The long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance is prepared from the following raw materials:
polypropylene PP60Kg
40Kg of glass fiber
5Kg of functional compatilizer
0.6Kg of lubricant
1.3Kg of antioxidant.
The preparation method of the long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance comprises the following steps:
s1, respectively weighing PP, a functional compatilizer, a lubricant and an antioxidant in proportion, and stirring in a high-speed stirrer for 10 minutes;
s2, adding the uniformly mixed material in the step S1 into a double-screw extruder for plasticizing;
s3, scattering the glass fibers by a glass fiber scattering device, wherein the rotating speed of the glass fiber scattering device is 30 rpm; baking at high temperature (90-110 deg.C, linear velocity of 1.0-1.5m/s, heating time of about 1 s) and making the obtained product be fed into impregnation die head; the glass fiber enters the impregnation die head and is drawn by a drawing machine, and the drawing speed is 400 rpm;
and S4, pressing the PP mixture plasticized after the S2 into a dipping die head through which glass fibers pass by using a screw extruder, and carrying out traction, cooling and grain cutting treatment to prepare the PP reinforced material with the length of 10-14mm, wherein the extrusion temperature and the temperature of the dipping die head are 220-240 ℃, and the rotating speed of a main machine of the extruder is 350 rpm.
The PP composite of this example was tested using ISO standards and the results are shown in table 3 below.
Table 3 test results of example 3
Example 4
The long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance is prepared from the following raw materials:
polypropylene PP70Kg
45Kg of glass fiber
5Kg of functional compatilizer
0.4Kg of lubricant
1.0Kg of antioxidant.
The preparation method of the long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance comprises the following steps:
s1, respectively weighing PP, a functional compatilizer, a lubricant and an antioxidant in proportion, and stirring in a high-speed stirrer for 9 minutes;
s2, adding the uniformly mixed material in the step S1 into a double-screw extruder for plasticizing;
s3, scattering the glass fibers by a glass fiber scattering device, wherein the rotating speed of the glass fiber scattering device is 35 rpm; baking in a high-temperature cabinet (90-110 ℃, linear speed of 1.0-1.5m/s and heating time of about 1 s) after scattering, and then feeding into an impregnation die head; the glass fiber enters the impregnation die head and is drawn by a drawing machine, and the drawing speed is 550 rpm;
and S4, pressing the PP mixture plasticized after the S2 into a dipping die head through which glass fibers pass by using a screw extruder, and carrying out traction, cooling and grain cutting treatment to prepare the PP reinforced material with the length of 10-14mm, wherein the extrusion temperature and the temperature of the dipping die head are 220-240 ℃, and the rotating speed of a main machine of the extruder is 360 rpm.
The PP composite of this example was tested using ISO standards and the results are shown in table 4 below.
Table 4 test results of example 4
Comparative example 1
Different from the embodiment 1, the extrusion temperature and the impregnation die head temperature of the double-screw extruder are 260-280 ℃, and other conditions are not changed. The temperature is increased here in order to increase the flowability of the plastic mass and to produce a better wetting and coating action.
The PP composite of this example was tested using ISO standards and the results are shown in table 5 below.
Table 5 test results of comparative example 1
The extrusion temperature of the double-screw extruder and the temperature of the dipping die head of the comparative example are 260-280 ℃, and other conditions are unchanged. Compared with example 1, the odor intensity of this comparative example is ultra-high because the molecular chain of polypropylene is broken due to the increase of temperature, the mechanical property of the material is reduced, and some volatile small molecules are generated, resulting in heavy odor.
Comparative example 2
Unlike example 1, the grafting ratio of the compatibilizer, maleic anhydride grafted polypropylene, was 0.8%. Other conditions were unchanged. The PP composite of this comparative example was tested using ISO standards and the results are given in table 6 below.
Table 6 test results of comparative example 2
The maleic anhydride-grafted polypropylene used in this comparative example had a grafting ratio of 0.8%, and the other conditions were unchanged. Compared with example 1, the floating fiber of the comparative example has ultrahigh odor intensity, low grafting rate of maleic anhydride, high monomer residual amount and larger odor.
Comparative example 3
Different from the embodiment 1, the rotating speed of the glass fiber scattering device is 5rpm, and the glass fiber is not heated by high-temperature baking. Other conditions were unchanged.
The PP composite of this comparative example was tested using ISO standards and the results are given in table 7 below.
Table 7 test results of comparative example 3
The glass fiber of the comparative example is not baked at high temperature, the rotating speed of the scattering device is reduced, the glass fiber cannot be scattered and enters the impregnation die head in a cluster shape, polypropylene cannot be completely infiltrated into the glass fiber, the compatibility effect is poor, and the mechanical property is seriously reduced. Parts made by injection molding of this material are highly likely to exhibit fiber floating.
Comparative example 4
Unlike example 1, the amount of antioxidant added was changed from 1.2Kg to 0.4 Kg. Other conditions were unchanged.
The PP composite of this comparative example was tested using ISO standards and the results are given in table 8 below.
Table 8 test results of comparative example 4
The antioxidant of the comparative example has low addition amount and little change of mechanical properties, but the mechanical properties are seriously reduced after long-term heat aging.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance is characterized by comprising the following raw materials in parts by weight:
50-70 parts of polypropylene PP
30-50 parts of long glass fiber
3-15 parts of functional compatilizer
0.2 to 1 part of lubricant
0.7-1.5 parts of antioxidant;
the long glass fiber is pretreated alkali-free continuous glass fiber, and the diameter of the long glass fiber is 11-20 mu m; the total coating angle of the continuous glass fiber is 270 degrees, and the fiber tension is 25-30N;
in the preparation process, continuous glass fibers are scattered by a glass fiber scattering device, wherein the rotating speed of the glass fiber scattering device is 18-35 rpm; baking the scattered materials in a high-temperature cabinet, then feeding the baked materials into an impregnation die head, and impregnating and coating the extruded molten PP mixture in the impregnation die head; and the continuous glass fiber enters the impregnation die head and is drawn by a drawing machine, and the drawing speed is 350-600 rpm.
2. The low odor, low fiber floating, heat aging resistant long glass fiber reinforced polypropylene material of claim 1, wherein the glass fibers are pre-treated by:
a. soaking the continuous glass fiber into an acrylic acid or acrylate solution for 8-12 h at the temperature of 30-65 ℃; b. and naturally airing the soaked continuous glass fiber, and drying in a drying oven at 150 ℃ for later use.
3. The low odor, low fiber floating, heat aging resistant long glass fiber reinforced polypropylene material of claim 1, wherein the PP is a specific type of block copolymer PP or a mixture of different types of block copolymer PP, and the melt index is greater than 70g/10 min.
4. The low odor, low fiber floating, heat aging resistant long glass fiber reinforced polypropylene material of claim 3, wherein the PP is a block copolymer PP of a specific type and has a melt index of 100g/10 min.
5. The low-odor, low-fiber-floating and heat-aging-resistant long glass fiber reinforced polypropylene material as claimed in claim 1, wherein the antioxidant is one or a mixture of several of an antioxidant 1010, an antioxidant 1076, an antioxidant 168 and an antioxidant AO-412S, preferably a mixture of the antioxidant 1010, the antioxidant 168 and the antioxidant AO-412S in a weight ratio of 2:1: 4.
6. The low odor, low fiber floating, heat aging resistant long glass fiber reinforced polypropylene material of claim 1, wherein the lubricant is one or a mixture of more of lubricant EBS, lubricant PETS and silicone powder.
7. The low-odor, low-floating-fiber, heat-aging-resistant long glass fiber reinforced polypropylene composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
56 parts of polypropylene PP
40 portions of glass fiber
4 portions of functional compatilizer
0.5 part of lubricant
1.2 parts of antioxidant.
8. The low odor, low fiber floating, heat aging resistant long glass fiber reinforced polypropylene material of claim 1, wherein the functional compatibilizer is maleic anhydride grafted polypropylene (PP-g-MAH), wherein the grafting ratio of the maleic anhydride grafted polypropylene is not less than 1%, and the mass fraction of maleic anhydride is 2%.
9. The process for preparing a low odor, low fiber floating, heat aging resistant long glass fiber reinforced polypropylene material of any of claims 1 to 8, comprising the steps of:
s1, respectively weighing the polypropylene PP, the functional compatilizer, the lubricant and the antioxidant in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
s2, adding the uniformly mixed material in the step S1 into a double-screw extruder for plasticizing;
and S3, pressing the PP mixture plasticized after the S2 into a dipping die head through which continuous glass fibers pass by using a screw extruder, and preparing the PP reinforced material with the length of 10-14mm through traction, cooling and grain cutting treatment.
10. The process for preparing the low odor, low fiber floating, heat aging resistant long glass fiber reinforced polypropylene material according to claim 9, wherein the twin screw extruder is used under the following conditions: the extrusion temperature and the temperature of the dipping die head are 220-240 ℃, and the rotating speed of the extruder host is 300-420 rpm.
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| CN114770804A (en) * | 2022-04-28 | 2022-07-22 | 常州威材新材料科技有限公司 | Processing technology of PP-LFT material |
| CN115011041A (en) * | 2022-07-15 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Environment-friendly high-gloss low-floating-fiber continuous reinforced long glass fiber polypropylene composite material |
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| JPH07267689A (en) * | 1994-03-31 | 1995-10-17 | Mitsubishi Rayon Co Ltd | Polymer-coated glass fiber and its production |
| CN101338051B (en) * | 2008-08-08 | 2010-12-15 | 苏州工业园区和昌电器有限公司 | Long glass fiber reinforced polypropylene material and preparation thereof |
| CN101474868B (en) * | 2008-10-15 | 2011-02-02 | 上海杰事杰新材料股份有限公司 | Equipment for preparing continuous fiber reinforced thermoplastic resin composite material presoaked belt and use thereof |
| CN202298179U (en) * | 2011-11-09 | 2012-07-04 | 台州市家得宝日用品有限公司 | Continuous fiber dispersing device |
| CN103589103B (en) * | 2012-08-14 | 2018-07-13 | 合肥杰事杰新材料股份有限公司 | A kind of Long Glass Fiber Reinforced PP Composite, preparation method and applications |
| CN106626444A (en) * | 2016-07-27 | 2017-05-10 | 山东极威新材料科技有限公司 | Production technology of continuous fiber reinforced thermoplastic composites (CFRTP) pultruded profiles |
| CN109679218A (en) * | 2018-12-28 | 2019-04-26 | 重庆普利特新材料有限公司 | A kind of low smell high-performance Long Glass Fiber Reinforced PP Composite and preparation method thereof |
| CN110041609A (en) * | 2019-04-28 | 2019-07-23 | 东风汽车集团有限公司 | A kind of low floating fine continuously Long Glass Fiber Reinforced PP Composite and the preparation method and application thereof |
| CN110698757B (en) * | 2019-10-09 | 2022-02-01 | 中广核俊尔(浙江)新材料有限公司 | Continuous glass fiber reinforced polypropylene unidirectional prepreg tape material and preparation method and application thereof |
| CN110964270B (en) * | 2019-12-19 | 2022-08-09 | 天津金发新材料有限公司 | High-impact-resistance long glass fiber reinforced SAN (styrene-Acrylonitrile) composition as well as preparation method and application thereof |
| CN111410789A (en) * | 2020-04-14 | 2020-07-14 | 重庆国际复合材料股份有限公司 | Low-odor low-VOC glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN112724526A (en) * | 2020-12-29 | 2021-04-30 | 上海普利特复合材料股份有限公司 | Low-agglomeration long glass fiber reinforced polypropylene composite material for automotive interior and preparation method thereof |
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| CN114770804A (en) * | 2022-04-28 | 2022-07-22 | 常州威材新材料科技有限公司 | Processing technology of PP-LFT material |
| CN114770804B (en) * | 2022-04-28 | 2024-02-02 | 常州威材新材料科技有限公司 | Processing technology of PP-LFT material |
| CN115011041A (en) * | 2022-07-15 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Environment-friendly high-gloss low-floating-fiber continuous reinforced long glass fiber polypropylene composite material |
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