CN114479283B - Long glass fiber reinforced polypropylene composite material and preparation method and application thereof - Google Patents

Long glass fiber reinforced polypropylene composite material and preparation method and application thereof Download PDF

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CN114479283B
CN114479283B CN202011163308.XA CN202011163308A CN114479283B CN 114479283 B CN114479283 B CN 114479283B CN 202011163308 A CN202011163308 A CN 202011163308A CN 114479283 B CN114479283 B CN 114479283B
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polypropylene
glass fiber
fiber reinforced
parts
long glass
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CN114479283A (en
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李长金
张师军
高达利
徐凯
尹华
邵静波
孙昌辉
谭以纲
侴白舸
王宇韬
任月明
吕芸
白弈青
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08J2323/14—Copolymers of propene
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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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    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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Abstract

The invention relates to a long glass fiber reinforced polypropylene composite material in the field of high polymer materials, and a preparation method and application thereof. The long glass fiber reinforced polypropylene composite material comprises the following components in parts by weight: 100 parts of polypropylene; 3-15 parts of a compatilizer composition; 20-60 parts of glass fiber; 3-25 parts of a surface modifier; the melt flow rate of the polypropylene is 40-150g/10min under the conditions of 230 ℃ and a load of 2.16 kg; the long glass fiber reinforced polypropylene composite material reduces the glass fiber floating fiber phenomenon on the basis of maintaining the corrosion resistance and high tensile strength of the glass fiber material, improves the impact strength and the flow property of the material, accelerates the melting process of the material, and well optimizes the processing property.

Description

Long glass fiber reinforced polypropylene composite material and preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a long glass fiber reinforced polypropylene composite material, a preparation method and application thereof.
Background
Polypropylene is a thermoplastic resin made by polymerization of propylene. Polypropylene is a non-toxic, odorless and tasteless milky high crystalline polymer, and is one of the lightest varieties in all plastics at present. It is stable to water, and has good forming property, but because of the large shrinkage rate and the easy sinking of thick-wall products, it is difficult to meet the requirements for some parts with higher dimensional accuracy, and the surface gloss of the products is good. The polypropylene has high crystallinity and regular structure, so that the polypropylene has excellent mechanical properties. The polypropylene has good chemical stability, and can be corroded by concentrated sulfuric acid and concentrated nitric acid, and is relatively stable to other various chemical reagents. Has good dielectric property and high-frequency insulation property, is not affected by humidity, but becomes brittle at low temperature, is not wear-resistant and is easy to age. Is suitable for manufacturing general mechanical parts, corrosion-resistant parts and insulating parts.
The polypropylene glass fiber composite material is prepared by adding glass fiber and other auxiliary agents on the basis of original polypropylene, thereby improving the application range of the material. After the glass fiber is reinforced, the glass fiber is a high-temperature resistant material, so that the heat-resistant temperature of polypropylene is greatly improved compared with that before the glass fiber is not added. After the glass fiber is reinforced, the mutual movement among the polymer chains is limited due to the addition of the glass fiber, so that the shrinkage rate of the polypropylene is greatly reduced, and the rigidity is also greatly improved. After the glass fiber is reinforced, the polypropylene can not crack stress, and the impact resistance is improved greatly. The strength of the plastic is also greatly improved after the glass fiber is reinforced. With the rapid development of the modern automobile industry, the trend of environmental protection and low carbon is more obvious, and the weight reduction of automobiles has been increased to the national strategy level. The application of lightweight materials is not separated from the achievement of the aim of automobile lightweight, the automobile lightweight is realized by using a plastic steel technology, and the automobile lightweight material is a hot spot for the application research of new automobile materials and is a necessary trend of automobile development. The long glass fiber reinforced polypropylene composite material has become one of the main materials for plastic steel substitution in the automobile industry by virtue of excellent material performance, excellent weight reduction effect and higher cost performance. In practical application, the plastic can replace steel and reinforced engineering plastics, and the use requirements of the fields of packaging boxes, household appliances, electronics, electrics, transportation and the like are met.
However, the existing long glass fiber reinforced polypropylene material has some defects in the practical application process. For example, the surface quality of the long glass fiber reinforced polypropylene material product is low, namely the surface floating fiber is a problem; particularly in the application of large complex parts of automobiles, the problems of high strength, high impact and other material performance requirements, high flow, easy molding processing requirements, high surface quality of molded products and the like are faced. The application range of the glass fiber reinforced polypropylene material is directly limited by the occurrence of the problems.
Chinese patent CN201110008670 discloses a high-impact-resistance low-fiber-floating long glass fiber reinforced polypropylene material, which has the advantages of high surface gloss, less fiber-floating phenomenon and good drop resistance of the prepared polypropylene material. Chinese patent CN201610207016 discloses a flame retardant and toughening polypropylene blend material with high finish and long glass fiber, which is suitable for middle and high end furniture articles with high requirements on product structure, appearance, cost and processability. The above patents all mainly reduce the interaction force between the surface of the die and the melt through the anti-floating fiber agent, so as to reduce the phenomenon of floating fiber on the surface of the part as much as possible. Chinese patent CN201510681645 discloses a long glass fiber with low floating fiber and a high impact resistance PP composite material containing the long glass fiber, and the glass fiber is pretreated with hydrogen peroxide and potassium nitrate and then reused, which has the advantages of excellent impact resistance, smooth surface and no floating fiber, and is especially suitable for preparing products such as automobile parts, electronic product shells, etc. But the content of glass fiber in the prepared material is lower than 5-10 parts.
At present, a composite material which can improve the surface quality of a workpiece and simultaneously has comprehensive mechanical properties and molding processability is required in the market.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a long glass fiber reinforced polypropylene composite material. In particular to a long glass fiber reinforced polypropylene composite material and a preparation method thereof.
The long glass fiber reinforced polypropylene composite material prepared by the method reduces the glass fiber floating fiber phenomenon on the basis of maintaining the corrosion resistance and high tensile strength of the glass fiber material, improves the impact strength and the flow property of the material, and optimizes the processing property of the material.
The invention aims at providing a long glass fiber reinforced polypropylene composite material which can be prepared from the following components in parts by weight:
100 parts of polypropylene;
3-15 parts of a compatilizer composition; preferably 3-10 parts;
20-60 parts of glass fiber; preferably 30-50 parts;
3-25 parts of a surface modifier; preferably 5-10 parts.
Wherein,,
the polypropylene may be a high flow polypropylene;
the polypropylene can be at least one of isotactic polypropylene, syndiotactic polypropylene and atactic polypropylene. The polypropylene may be a copolymerized or a homopolymerized polypropylene.
Further, the polypropylene may have a melt flow rate of 40 to 150g/10min, preferably 100 to 150g/10min, at 230℃under a load of 2.16kg.
The compatibilizer composition may comprise a mixture of maleic anhydride grafted polypropylene and bisphenol a diglycidyl ether, wherein the weight ratio of maleic anhydride grafted polypropylene to bisphenol a diglycidyl ether may be 1:2 to 5:1, preferably 1:1 to 3:1, more preferably 1:1 to 2:1. The bisphenol a diglycidyl ether may be specifically selected from 903H.
The preparation method of the compatilizer composition specifically comprises the following steps: mixing the maleic anhydride grafted polypropylene and bisphenol A diglycidyl ether (solid state) according to the dosage. The mixing can be carried out at normal temperature, in particular at 30-50 ℃.
Wherein the density of the maleic anhydride grafted polypropylene can be 0.89-0.91 g/cm 3 The melting point may be 160-180 ℃, the melt flow rate (230 ℃,2.16 Kg) may be 100-200 g/10min, and the grafting ratio of maleic anhydride may be 0.8-1.2%.
The bisphenol A diglycidyl ether can have a melt viscosity of 3000-15000mPa.s and a softening point temperature of 88-98 ℃.
The surface modifier can be at least one of ultra-high melt index polypropylene;
preferably, the ultra-high melt polypropylene has a melt flow rate of 150-10000g/10min, preferably 400-3800g/10min, more preferably 1000-2000g/10min.
More preferably, the surfactant may be: the polypropylene with the melt index of 1000-10000 g/10min is mixed with the polypropylene with the melt index of 150-999 g/10min, wherein the dosage range of the polypropylene with the melt index of 1000-10000 g/10min and the polypropylene with the melt index of 150-999 g/10min is (5-1): (1-5), preferably (2-1): (1-2).
The glass fiber can be alkali-free high-strength continuous glass fiber, the strength is more than 2300MPa, the diameter is 10-24 um, and the linear density is 1200-4800 TEX; specifically, the glass fiber may be selected from at least one of model numbers 362J, T838T, 362K, SE4805D, ER 4305.
Preferably, the long glass fiber reinforced polypropylene composite material described herein may further comprise a lubricant; wherein, the dosage of the lubricant is 0.5 to 1 weight part based on 100 weight parts of the polypropylene; and/or the lubricant can be at least one of oxidized polyethylene wax and microcrystalline paraffin wax.
Preferably, an antioxidant can be added in the invention, and the dosage of the antioxidant is 0.1-3 parts by weight based on 100 parts by weight of the polypropylene; specifically, the antioxidant can be one or two of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, antioxidant 626 or antioxidant 636.
The invention adds the combination of the maleic anhydride grafted polypropylene and the bisphenol A diglycidyl ether as the compatilizer, and the high-activity epoxy group in the bisphenol A diglycidyl ether can be coupled with hydroxyl, amino and other groups of the maleic anhydride grafted polypropylene, thereby enhancing the interface bonding strength of glass fiber and polypropylene resin together and finally improving the comprehensive mechanical property of the material; and the bisphenol A diglycidyl ether has better fluidity than a matrix, so that the bisphenol A diglycidyl ether has a certain positive effect on improving the glossiness of the material, and meanwhile, the invention is compounded with a proper amount of ultra-high melt index and low molecular weight polypropylene as a surface modifier, so that the surface quality of a finished product is improved.
Other adjuvants commonly used in the art can be added to the present invention without adversely affecting the properties of the matrix resin, including but not limited to at least one of slip agents, antistatic agents, plasticizers, and the like. In addition, the amounts of the other adjuvants are all conventional in the art and will be known to those skilled in the art.
The second purpose of the invention is to provide a preparation method of the long glass fiber reinforced polypropylene composite material, which comprises the following steps:
and mixing the components comprising the polypropylene, the compatilizer composition and the surface modifier to obtain polypropylene mixed resin, and then carrying out dipping coating on the polypropylene mixed resin and glass fiber by adopting a full-dipping method to obtain the long glass fiber reinforced polypropylene composite material.
Specifically, the preparation method of the long glass fiber reinforced polypropylene composite material can comprise the following steps:
mixing components comprising the polypropylene, a compatilizer composition and a surface modifier to obtain polypropylene mixed resin; and then, carrying out dipping cladding on the molten polypropylene mixed resin and the glass fibers after preheating and dispersing to obtain the long glass fiber reinforced polypropylene composite material.
More specifically, the preparation method of the long glass fiber reinforced polypropylene composite material can comprise the following steps:
(1) Adding the components comprising the polypropylene, the compatilizer composition, the antioxidant, the lubricant and the surface modifier into a high-speed mixer, and adding the mixed polypropylene mixed resin into a hopper of an extruder for standby. The mixing temperature can be controlled to be 40-60 ℃, and the mixing time can be 3-5 minutes.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene composite material. The size of the orifice template is selected to adjust the content of the continuous glass fiber in the composite material to 20-60 parts; and (3) obtaining the long glass fiber reinforced polypropylene granules with the grain cutting length of 6-25 mm by adjusting the rotating speed of a cutter of a grain cutting machine.
Wherein, the extruder can be a double screw extruder, the screw diameter can be 40-55 mm, and the length-diameter ratio of the screw can be 40:1, the processing temperature can be 230-280 ℃, the melt temperature can be 230-260 ℃ and the machine head temperature can be 240-280 ℃.
The temperature of the impregnating device can be 220-230 ℃.
The temperature of the dispersion roller system and the preheating unit can be 130-170 ℃.
The size of the mouth template of the shaping mouth template is 3.0-5.0 mm, which corresponds to 20-60 parts of glass fiber in the composite material.
The invention also provides application of the long glass fiber reinforced polypropylene composite material or the long glass fiber reinforced polypropylene composite material prepared by the preparation method in the fields of automobiles, electronics, electrics, household appliances and transportation.
The long glass fiber reinforced polypropylene composite material reduces the glass fiber floating fiber phenomenon on the basis of keeping the corrosion resistance and high tensile strength of the glass fiber material, improves the impact strength and the flow property of the material, accelerates the melting process of the material, and well optimizes the processing property.
Detailed Description
The invention will be further illustrated with reference to the following examples. The present invention is not limited by these examples.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Raw material source
The polypropylene is high-flow copolymerized polypropylene, the comonomer is ethylene, the vinyl content is 2-4 mol%, the melt flow rate is 110g/10min, and the test condition is 230 ℃ and 2.16Kg.
Glass fiber: alkali-free glass fiber, SE4805D, diameter of 17 μm and linear density of 2400tex.
Maleic anhydride graftingPolypropylene (PP-g-MAH), BONDYRAM 1001, pr Li Lang plastics industries, inc. (grafting anhydride content 1%, melting point 160 ℃ C., density 0.9 g/cm) 3 Melt flow Rate 100g/10 min)
Bisphenol A diglycidyl ether, brand 903H, melt viscosity 3000-15000mPa.s, softening point temperature 88-98 ℃, commercially available from Shanghai curing company, inc.;
antioxidant 1010, manufactured by basf corporation;
antioxidant 168, manufactured by basf corporation;
surface modifier, PP, PF1500, melt index 1500g/min, available from Hunan Shenggan New Material Co., ltd;
the surface modifier, PP, PPH-Y450 and melt index 450g/min are purchased from China petrochemical stone village;
microcrystalline Paraffin No. 80, china petrochemical Vitex division.
Example 1:
(1) Weighing 100 parts by weight of dried polypropylene, 6 parts by weight of a composition prepared by maleic anhydride grafted polypropylene 1001 and 903H according to a weight ratio of 2:1, 5 parts by weight of a surface modifier prepared by PF1500 and PPH-Y450 according to a weight ratio of 1:1, 0.1 part by weight of an antioxidant and 0.5 part by weight of a lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene mixed resin into a hopper of a double-screw extruder for standby.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 40 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Comparative example 1:
(1) Weighing 100 parts by weight of dried polypropylene, 6 parts by weight of maleic anhydride grafted polypropylene 1001, 0.1 part by weight of antioxidant and 0.5 part by weight of lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene resin into a hopper of a double-screw extruder for later use;
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 40 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Comparative example 2:
(1) Weighing 100 parts by weight of dried polypropylene, 6 parts by weight of a mixture prepared by maleic anhydride grafted polypropylene 1001 and 903H according to a weight ratio of 2:1, 0.1 part by weight of an antioxidant (obtained by mixing and compounding antioxidant 1010 and antioxidant 168 according to a weight ratio of 1:1) and 0.5 part by weight of a lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene mixed resin into a hopper of a double-screw extruder for standby.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 40 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Comparative example 3:
(1) Weighing 100 parts by weight of dried polypropylene, 6 parts by weight of maleic anhydride grafted polypropylene 1001, 5 parts by weight of PF1500 and PPH-Y450, preparing a surface modifier according to a weight ratio of 1:1, 0.1 part by weight of antioxidant and 0.5 part by weight of lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene mixed resin into a hopper of a double-screw extruder for standby.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 40 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Example 2:
(1) Weighing 100 parts by weight of dried polypropylene, 6 parts by weight of a mixture prepared by maleic anhydride grafted polypropylene 1001 and 903H according to a weight ratio of 2:1, 10 parts by weight of a surface modifier prepared by PF1500 and PPH-Y450 according to a weight ratio of 1:1, 0.1 part by weight of an antioxidant and 0.5 part by weight of a lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene mixed resin into a hopper of a double-screw extruder for standby.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 40 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Example 3:
(1) Weighing 100 parts by weight of dried polypropylene, 6 parts by weight of a composition prepared by maleic anhydride grafted polypropylene 1001 and 903H according to a weight ratio of 1:1, 5 parts by weight of a surface modifier prepared by PF1500 and PPH-Y450 according to a weight ratio of 1:1, 0.1 part by weight of an antioxidant and 0.5 part by weight of a lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene mixed resin into a hopper of a double-screw extruder for standby.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 40 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Example 4:
(1) Weighing 100 parts by weight of dried polypropylene, 3 parts by weight of a composition prepared by maleic anhydride grafted polypropylene 1001 and 903H according to a weight ratio of 2:1, 5 parts by weight of a surface modifier prepared by PF1500 and PPH-Y450 according to a weight ratio of 1:1, 0.1 part by weight of an antioxidant and 0.5 part by weight of a lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene mixed resin into a hopper of a double-screw extruder for standby.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 30 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Example 5:
(1) Weighing 100 parts by weight of dried polypropylene, 8 parts by weight of a composition prepared by maleic anhydride grafted polypropylene 1001 and 903H according to a weight ratio of 2:1, 10 parts by weight of a surface modifier prepared by PF1500 and PPH-Y450 according to a weight ratio of 1:1, 0.1 part by weight of an antioxidant and 0.5 part by weight of a lubricant, stirring in a high-speed mixer for 3min, and adding the mixed polypropylene mixed resin into a hopper of a double-screw extruder for standby.
(2) And (3) adopting continuous fiber reinforced thermoplastic material impregnating equipment, and feeding the polypropylene mixed resin mixed in the step (1) into a melting impregnating die connected with an extruder head after melting and plasticizing the polypropylene mixed resin through an extruder.
(3) And (3) guiding the continuous glass fiber bundles out of the fiber guiding frame, entering a glass fiber dispersing roller system and a preheating unit to preheat and disperse the glass fibers, then entering a melting dipping die head, and carrying out dipping cladding with melted polypropylene mixed resin.
(4) The impregnated and coated composite material strip is pulled out through a shaping plate and a mouth template, and is subjected to bracing, cooling, blow-drying and granulating to prepare the long glass fiber reinforced polypropylene prepreg. The size of the port template is selected to adjust the content of the continuous glass fiber in the composite material to 50 parts by weight; the long glass fiber reinforced polypropylene prepreg with the grain cutting length of 12mm is obtained by adjusting the rotating speed of a cutter of a grain cutting machine.
(5) And (5) drying the prepreg, and performing injection molding to perform performance test.
Performance test:
the performance test methods of examples 1 to 5 and comparative examples 1 to 3 are as follows:
the tensile strength is measured according to ISO527-2, the tensile speed is 5mm/min;
the bending strength is detected according to ISO178 standard, and the bending speed is 2mm/min;
notched impact strength was measured according to ISO179 standard;
the density test is carried out according to the ISO1183 standard;
ash content is detected according to GB/T9345 standard;
the fluidity is detected according to an Archimedes spiral measuring method of plastic flow property, the injection molding speed is 50.0mm/s, the maximum injection pressure is 1028Bar, the melt temperature is 245 ℃, and the mold temperature is 70 ℃;
the surface gloss was measured according to ISO2813 standard.
The material property test results are shown in Table 1:
TABLE 1 Material Performance test results
Remarks:
product surface quality comparison (visual surface quality): the number of the first five times is equal to the first five times, general key of the invention
Product surface quality comparison (visual processability): the number of the first five times is equal to the first five times, general key of the invention
In the invention, the composition of the maleic anhydride grafted polypropylene and the bisphenol A diglycidyl ether is added as a compatilizer, and the high-activity epoxy group is coupled with hydroxyl, amino and other groups, so that the compatibility between the polypropylene and the glass fiber is enhanced together, and the interface bonding strength is improved; meanwhile, the ultra-high melt index and the low molecular polypropylene are added as the surface modifier, so that the flowing state in the composite material mold during injection molding is changed, meanwhile, the matrix polypropylene resin is endowed with better fluidity, and the surface quality of a sample is improved.
As can be seen from the comparison of the above examples with the comparative examples, the composition of maleic anhydride grafted polypropylene and bisphenol A diglycidyl ether was used as a compatibilizer to improve the tensile strength, flexural modulus and notched impact strength of the composite; the ultra-high melt index and low molecular weight polypropylene are used as the surface modifier, so that the surface glossiness and the surface quality of the sample piece are improved. The long glass fiber reinforced polypropylene composite material optimizes the surface quality, comprehensive mechanical property and processing property of the material.

Claims (14)

1. The long glass fiber reinforced polypropylene composite material comprises the following components in parts by weight:
100 parts of polypropylene;
3-15 parts of a compatilizer composition;
20-60 parts of glass fiber;
3-25 parts of a surface modifier;
the polypropylene is high-flow polypropylene; the melt flow rate of the polypropylene is 40-150g/10min under the conditions of 230 ℃ and a load of 2.16 kg;
the compatilizer composition is a combination of maleic anhydride grafted polypropylene and bisphenol A diglycidyl ether; wherein the weight ratio of the maleic anhydride grafted polypropylene to the bisphenol A diglycidyl ether is 1:2-5:1;
the surface modifier is ultra-high melt index polypropylene; the melt flow rate of the ultra-high melt index polypropylene is 400-3800g/10 min.
2. The long glass fiber reinforced polypropylene composite material according to claim 1, which is characterized by comprising the following components in parts by weight:
100 parts of polypropylene;
3-10 parts of a compatilizer composition;
30-50 parts of glass fiber;
5-10 parts of a surface modifier.
3. The long glass fiber reinforced polypropylene composite of claim 1, wherein:
the melt flow rate of the polypropylene is 100-150g/10min under the conditions of 230 ℃ and a load of 2.16kg.
4. The long glass fiber reinforced polypropylene composite of claim 1, wherein:
the polypropylene is at least one selected from isotactic polypropylene, syndiotactic polypropylene and atactic polypropylene.
5. The long glass fiber reinforced polypropylene composite of claim 1, wherein:
the weight ratio of the maleic anhydride grafted polypropylene to the bisphenol A diglycidyl ether is 1:1-3:1.
6. The long glass fiber reinforced polypropylene composite of claim 1, wherein:
the density of the maleic anhydride grafted polypropylene is 0.89-0.91 g/cm 3 The melting point is 160-180 ℃, and the grafting rate of maleic anhydride is 0.8-1.2%.
7. The long glass fiber reinforced polypropylene composite of claim 6, wherein:
the melt flow rate of the maleic anhydride grafted polypropylene is 100-200 g/10min.
8. The long glass fiber reinforced polypropylene composite of claim 1, wherein:
the melt viscosity of the bisphenol A diglycidyl ether is 3000-15000mPa.s, and the softening point temperature is 88-98 ℃.
9. The long glass fiber reinforced polypropylene composite according to claim 1 or 2, wherein:
the glass fiber is alkali-free high-strength continuous glass fiber, the strength is more than 2300MPa, the diameter is 10-24 um, and the linear density is 1200-4800 TEX.
10. The long glass fiber reinforced polypropylene composite according to claim 1 or 2, characterized by comprising a lubricant; wherein,,
the amount of the lubricant is 0.5 to 1 weight part based on 100 weight parts of the polypropylene; and/or the number of the groups of groups,
the lubricant is at least one of oxidized polyethylene wax and microcrystalline wax.
11. The method for producing a long glass fiber reinforced polypropylene composite material according to any one of claims 1 to 10, characterized by comprising the steps of:
and mixing the components comprising the polypropylene, the compatilizer composition and the surface modifier to obtain polypropylene mixed resin, and then carrying out dipping coating on the polypropylene mixed resin and glass fiber by adopting a full-dipping method to obtain the long glass fiber reinforced polypropylene composite material.
12. The method for preparing the long glass fiber reinforced polypropylene composite material according to claim 11, which is characterized by comprising the following steps:
(1) Mixing components comprising the polypropylene, a compatilizer composition and a surface modifier to obtain polypropylene mixed resin;
(2) And (3) carrying out dipping cladding on the molten polypropylene mixed resin and the glass fibers after preheating and dispersing to obtain the long glass fiber reinforced polypropylene composite material.
13. Use of the long glass fiber reinforced polypropylene composite according to any one of claims 1 to 10 or the long glass fiber reinforced polypropylene composite produced according to the production method of any one of claims 11 to 12 in the fields of electronics and electrical, household appliances and transportation.
14. The use according to claim 13, wherein the transportation field is an automotive field.
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