CN111849064A - Continuous glass fiber reinforced polypropylene prepreg tape and preparation method thereof - Google Patents
Continuous glass fiber reinforced polypropylene prepreg tape and preparation method thereof Download PDFInfo
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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
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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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- 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
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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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
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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
- C08J2453/00—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
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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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
Abstract
The invention discloses a continuous glass fiber reinforced polypropylene prepreg tape and a preparation method thereof, wherein the prepreg tape is prepared from the following raw materials: 30-70 parts of continuous glass fiber, 30-70 parts of polypropylene, 0.1-5 parts of compatilizer, 0.1-5 parts of antioxidant, 0.1-10 parts of lubricant, 0-5 parts of organic peroxide and 0.1-5 parts of nano silicon dioxide. The formula of the invention is scientific and reasonable, and the nano silicon dioxide is used for producing the continuous glass fiber reinforced polypropylene prepreg tape, so that the micron gap between glass fibers can be filled, the porosity of a composite material is greatly reduced, the combination of a compatilizer and the glass fibers can be promoted, the interface fastness of a resin system and the glass fibers is enhanced, and the continuous glass fiber reinforced polypropylene prepreg tape with better toughness, strength and surface smoothness is prepared.
Description
Technical Field
The invention relates to the field of composite material plates, in particular to a continuous glass fiber reinforced polypropylene prepreg tape and a preparation method thereof.
Technical Field
Because the performance of the composite material is improved along with the increase of the length of the reinforcing fiber, the continuous glass fiber reinforced polypropylene composite material has extremely excellent mechanical property and can even replace metal materials in certain occasions. Compared with the polypropylene composite material taking the glass fiber felt, the short glass fiber or the long glass fiber as the reinforcing material, the glass fiber in the continuous glass fiber reinforced polypropylene composite material is arranged in a unidirectional mode, and the continuous glass fiber reinforced polypropylene composite material has higher strength, modulus, fracture toughness and excellent creep resistance.
The physical properties of continuous glass fiber reinforced polypropylene composites are mainly affected by the flow properties of the polymer melt and the interfacial bonding state of the polypropylene resin and the glass fibers. The flow property of the polymer melt influences the impregnation condition of the polypropylene resin and the glass fiber, and the physical property of the continuous glass fiber reinforced polypropylene composite material can be improved by sufficient impregnation; the interfacial bonding state of the polypropylene resin and the glass fiber directly affects the final performance of the continuous glass fiber reinforced polypropylene composite material.
In the preparation method of the continuous glass fiber reinforced polypropylene prepreg tape, the full impregnation of the resin and the glass fiber is ensured mainly by using the high-fluidity polypropylene resin or adding an auxiliary agent to increase the fluidity of the resin, so that the problem of full impregnation of the polypropylene resin and the glass fiber is solved. The method of adding a compatilizer to a composite material system is commonly adopted by those skilled in the art, so that the bonding state of the interface of the polypropylene resin and the glass fiber is enhanced. Patent CN 105670107 a discloses a continuous glass fiber reinforced polypropylene composite material with high surface tension and a preparation method thereof, the method uses maleic anhydride grafted polypropylene as a compatilizer, and the bending strength of the prepared continuous glass fiber reinforced polypropylene composite material exceeds 150MPa, but the composite material has high porosity due to the weak combination of resin and glass fiber, and microscopic microscopy shows that the resin and the glass fiber are not completely organically combined, which affects the final properties of the material. Although the addition of the compatilizer to the composite material system can enhance the bonding state of the polypropylene resin and the glass fiber interface to a certain extent, the prepared composite material still has high porosity, and the performance of the composite material is influenced.
Disclosure of Invention
The invention provides a continuous glass fiber reinforced polypropylene prepreg tape and a preparation method thereof, aiming at solving the problems of high porosity and poor combination of resin and glass fiber of a continuous glass fiber reinforced polypropylene composite material.
The micron pores of the continuous glass fiber reinforced polypropylene prepreg tape are filled, the bonding fastness of resin and glass fiber is high, the porosity of the composite material is small, the thermal stability, toughness, strength and surface smoothness of the material are good, and the performance of the composite material is excellent.
The invention is realized by the following specific scheme:
on one hand, the invention provides a continuous glass fiber reinforced polypropylene prepreg tape, which comprises the following raw materials in parts by weight: 30-70 parts of continuous glass fiber, 30-70 parts of polypropylene, 0.1-5 parts of compatilizer, 0.1-5 parts of antioxidant, 0.1-10 parts of lubricant, 0-5 parts of organic peroxide and 0.1-5 parts of nano silicon dioxide.
The continuous glass fiber reinforced polypropylene prepreg tape has a scientific and reasonable formula, and a proper amount of nano silicon dioxide is introduced, so that micron pores among glass fibers can be filled, the porosity of a composite material is greatly reduced, the bonding fastness of resin and the glass fibers can be enhanced, the thermal stability, the toughness, the strength and the surface smoothness of the material are improved, and the performance of the composite material is improved.
Preferably, the particle size of the nano silicon dioxide is 10-50000 nm.
Preferably, the specific surface area of the nano silicon dioxide is 10-500 m/g.
The nano silicon dioxide with the particle size of 10-50000nm and the specific surface area of 10-500 m/g is used in the production of the continuous glass fiber reinforced polypropylene prepreg tape, so that micron gaps among glass fibers can be filled, the porosity of the composite material is greatly reduced, the combination of a compatilizer and the glass fibers can be promoted, and the interface fastness of a resin system and the glass fibers is enhanced.
Preferably, the continuous glass fiber is alkali glass twisted roving glass fiber; the linear density of the alkali glass stranded roving glass fiber is 100-10000 tex; the diameter of the alkali glass plied twistless roving glass fiber is 5-50 mu m.
Preferably, the polypropylene comprises one or more of homo-polypropylene, block co-polypropylene and random co-polypropylene.
Preferably, the lubricant comprises one or more of fatty acid amide lubricant, fatty acid ester lubricant, metal soap lubricant and silicone oil lubricant.
Preferably, the fatty acid amide lubricant is one or more of N, N-hexamethylene distearamide, oleamide and erucamide; the fatty acid ester lubricant is one or more of dibasic ester of saturated fatty alcohol, butyl stearate and glycerol trihydroxystearate; the metal soap lubricant is one or more of calcium stearate, zinc stearate and lead stearate; the silicone oil lubricant is one or more of dimethyl silicone oil, methyl phenyl silicone oil and dihexyl silicone oil.
Preferably, the organic peroxide comprises one or more of acyl peroxide, hydroperoxide, dialkyl peroxide and ester peroxide.
Preferably, the acyl peroxide is one or two of dibenzoyl peroxide and diisobutyryl peroxide; the hydroperoxide is one or two of peroxysuccinic acid and peroxyglutaric acid; the dialkyl peroxide is one or more of bis (tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and di-tert-butyl peroxide; the ester peroxide is one or two of tert-butyl peroxybenzoate and tert-butyl peroxypivalate.
Preferably, the gram weight of the prepreg tape is 100-1000 g/m2。
In another aspect, the present invention provides a method for preparing a continuous glass fiber reinforced polypropylene prepreg tape, comprising the steps of:
1) weighing the raw materials according to the required weight parts;
2) mixing and stirring the raw materials except the continuous glass fiber uniformly, and adding the mixture into a screw extruder to obtain a high-temperature melt; wherein the temperature of the screw extruder is set to: the first section is 180 ℃, the second section is 220 ℃, the third section is 240 ℃, the fourth section is 240 ℃ and the fifth section is 240 ℃;
3) Conveying the high-temperature melt into a pre-dipping die head, and enabling the high-temperature melt to enter a dipping die through the die head; wherein the temperature of the dipping die is set to be 240 ℃;
4) drawing the continuous glass fiber through an impregnation die, fully impregnating, rolling by a flattening roller with the air pressure of 0.3MPa and the temperature of 25 ℃, and cooling and forming to obtain a continuous glass fiber reinforced polypropylene prepreg tape; wherein the traction speed is 3-15 m/min.
The invention has the beneficial effects that: (1) the nano silicon dioxide can fill up micron gaps among glass fibers, and the porosity of the composite material is greatly reduced; (2) the nano silicon dioxide can promote the combination of the compatilizer and the glass fiber and enhance the interface fastness of the resin system and the glass fiber; (3) the prepared composite material has better toughness, strength and surface finish.
Detailed Description
The present invention is further illustrated by the following examples, which are illustrative of the present invention and are not to be construed as being limited thereto.
Example 1
A continuous glass fiber reinforced polypropylene prepreg tape and a preparation method thereof change the technical process as follows:
weighing raw materials according to the weight ratio, wherein the components and the ratio data are shown in table 1;
And step two, mixing and uniformly stirring the raw materials except the continuous glass fiber, adding the mixture into a screw extruder, wherein the temperature of the extruder is totally five sections, the first section is set to be 180 ℃, the second section is set to be 220 ℃, the third, fourth and fifth sections are set to be 240 ℃, conveying the high-temperature melt into a pre-dipping die head through the screw extruder, and entering an impregnation die through the die head, wherein the temperature of the impregnation die is totally five sections and is respectively set to be 240 ℃.
And step three, drawing the continuous glass fiber through a high-temperature dipping die at the speed of 3-15 m/min, fully dipping, drawing through a rolling device, and cooling and forming to obtain the continuous glass fiber reinforced polypropylene prepreg tape.
Examples 2 to 7
The raw materials of the components are weighed according to the weight proportion data provided in the table 1, and the rest of the implementation process is the same as that of the example 1.
Comparative examples 1 to 4
The raw materials of the components are weighed according to the weight proportion data provided in the table 1, and the rest of the implementation process is the same as that of the example 1.
TABLE 1 raw material formulations (unit is parts by weight) of examples 1 to 7 and comparative examples 1 to 4
In Table 1, polypropylene 8g/10min and 60g/10min are melt Mass Flow Rate (MFR) parameters.
The continuous glass fiber reinforced polypropylene prepreg tapes prepared in examples 1 to 7 and comparative examples 1 to 4 were cut into a size of 230 × 230mm, samples with a certain number of layers were placed in a forming mold in a crossed manner at 0 °/90 °, and a continuous glass fiber reinforced polypropylene composite board was prepared by a hot press. The resulting plate was carved using an engraving machine to test standard bars, and the tensile strength, flexural strength and modulus, interlaminar shear strength and notched impact strength of the test specimens were tested according to standards GB/T1447-2005, GB/T1449-2005, GB/T1451-2005 and JC/T733-2010, respectively, with the test results shown in Table 2.
TABLE 2 Performance test results of examples 1 to 7 and comparative examples 1 to 4
As can be seen from the test results of example 1 and comparative example 1, the incorporation of nanosilica into the composite material of the continuous glass fiber reinforced polypropylene prepreg tape can significantly improve the tensile strength, bending strength, interlaminar shear strength and notched impact strength of the composite material. The nano silicon dioxide is used for producing the continuous glass fiber reinforced polypropylene prepreg tape, so that micron gaps among glass fibers can be filled, the porosity of the composite material is greatly reduced, the combination of the compatilizer and the glass fibers can be promoted, and the interface fastness of a resin system and the glass fibers is enhanced, so that the continuous glass fiber reinforced polypropylene prepreg tape with more excellent mechanical properties is obtained.
As can be seen from the test results of examples 1 and 2 and comparative examples 1 and 2, the nano-silica has a significant enhancing effect on the performance of the composite material by using the polypropylene resin as the matrix of the composite material
The test results of the examples 2-5 and the comparative example 2 show that the performance of the composite material is obviously improved by changing the dosage and the specification of the nano silicon dioxide, and the nano silicon dioxide provided by the invention can be adjusted according to the actual conditions, so that the nano silicon dioxide has obvious interface optimization effect and performance enhancement effect.
As can be seen from the test results of examples 2 and 6 and comparative examples 2 and 3, the amount of the organic peroxide has a certain influence on the final performance of the continuous glass fiber reinforced polypropylene composite material product, but the reinforcing effect of the nano-silica on the performance of various composite material systems is more remarkable.
As can be seen from the test results of examples 2 and 7 and comparative examples 2 and 4, the use of different types of compatilizers also has a certain influence on the final performance of the continuous glass fiber reinforced polypropylene composite product, but the reinforcing effect of the nano-silica on the performance of various composite systems is still more remarkable.
The continuous glass fiber reinforced polypropylene prepreg tape has a scientific and reasonable formula, and the nano silicon dioxide is added, so that micron gaps among glass fibers can be filled, the porosity of a composite material is greatly reduced, the combination of a compatilizer and the glass fibers can be promoted, and the interface fastness of a resin system and the glass fibers is enhanced.
It should be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The continuous glass fiber reinforced polypropylene prepreg tape is characterized by comprising the following raw materials in parts by weight: 30-70 parts of continuous glass fiber, 30-70 parts of polypropylene, 0.1-5 parts of compatilizer, 0.1-5 parts of antioxidant, 0.1-10 parts of lubricant, 0-5 parts of organic peroxide and 0.1-5 parts of nano silicon dioxide.
2. The prepreg tape according to claim 1, wherein the nano silica has a particle size of 10 to 50000 nm.
3. The prepreg tape of claim 1, wherein the continuous glass fibers are alkali glass plied roving glass fibers; the linear density of the alkali glass stranded roving glass fiber is 100-10000 tex; the diameter of the alkali glass plied twistless roving glass fiber is 5-50 mu m.
4. The prepreg tape of claim 1, wherein the polypropylene comprises one or more of homo-polypropylene, block co-polypropylene, and random co-polypropylene.
5. The prepreg of claim 1, wherein the lubricant comprises one or more of a fatty acid amide type lubricant, a fatty acid ester type lubricant, a metal soap type lubricant, and a silicone oil type lubricant.
6. The prepreg according to claim 5, wherein the fatty acid amide-based lubricant is one or more of N, N-hexamethylene distearamide, oleamide and erucamide; the fatty acid ester lubricant is one or more of dibasic ester of saturated fatty alcohol, butyl stearate and glycerol trihydroxystearate; the metal soap lubricant is one or more of calcium stearate, zinc stearate and lead stearate; the silicone oil lubricant is one or more of dimethyl silicone oil, methyl phenyl silicone oil and dihexyl silicone oil.
7. The prepreg tape according to claim 1, wherein the organic peroxide comprises one or more of acyl peroxides, hydroperoxides, dialkyl peroxides, and ester peroxides.
8. The prepreg according to claim 7, wherein the acyl peroxide is one or both of dibenzoyl peroxide and diisobutyl peroxide; the hydroperoxide is one or two of peroxysuccinic acid and peroxyglutaric acid; the dialkyl peroxide is one or more of bis (tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and di-tert-butyl peroxide; the ester peroxide is one or two of tert-butyl peroxybenzoate and tert-butyl peroxypivalate.
9. The prepreg tape according to claim 1, wherein the grammage of the prepreg tape is 100 to 1000g/m2。
10. A preparation method of a continuous glass fiber reinforced polypropylene prepreg tape is characterized by comprising the following steps:
1) weighing the raw materials according to the required weight parts;
2) mixing and stirring the raw materials except the continuous glass fiber uniformly, and adding the mixture into a screw extruder to obtain a high-temperature melt; wherein the temperature of the screw extruder is set as follows: the first section is 180 ℃, the second section is 220 ℃, the third section is 240 ℃, the fourth section is 240 ℃ and the fifth section is 240 ℃;
3) conveying the high-temperature melt into a pre-dipping die head, and enabling the high-temperature melt to enter a dipping die through the die head; wherein the temperature of the dipping die is set to 240 ℃;
4) drawing the continuous glass fiber through an impregnation die, fully impregnating, rolling by a flattening roller with the air pressure of 0.3MPa and the temperature of 25 ℃, and cooling and forming to obtain a continuous glass fiber reinforced polypropylene prepreg tape; wherein the traction speed is 3-15 m/min.
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| CN113861555A (en) * | 2021-09-09 | 2021-12-31 | 振石集团华美新材料有限公司 | Continuous fiber reinforced thermoplastic prepreg tape and preparation method thereof |
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