CN114163692B - Glass fiber surface modification technology and application thereof in PA66 - Google Patents

Glass fiber surface modification technology and application thereof in PA66 Download PDF

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CN114163692B
CN114163692B CN202111370147.6A CN202111370147A CN114163692B CN 114163692 B CN114163692 B CN 114163692B CN 202111370147 A CN202111370147 A CN 202111370147A CN 114163692 B CN114163692 B CN 114163692B
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glass fiber
molecular weight
low molecular
surface modified
modified glass
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CN114163692A (en
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叶敬彪
赵学文
金英
卢勇
江枫
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Hengdian Group Debang Engineering Plastic Co ltd
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Hengdian Group Debang Engineering Plastic Co ltd
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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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/328—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/40—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/48—Coating with two or more coatings having different compositions
    • C03C25/50—Coatings containing organic materials only
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08K2201/004—Additives being defined by their length
    • 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
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    • C08K2201/005—Additives being defined by their particle size in general
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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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

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Abstract

The invention belongs to the technical field of high polymer materials and processing thereof, and discloses a glass fiber surface modification technology and application thereof in a PA66 material with high mechanical property. The glass fiber surface modification technology of the invention comprises the following steps: dissolving a double bond-containing coupling agent in a solvent 1 to prepare a solution, stirring and mixing glass fibers and the coupling agent solution, drying the mixture to obtain glass fibers with double bond functional groups on the surfaces, adding the glass fibers with the double bond functional groups on the surfaces, maleic anhydride and the solvent 2 into a reaction container, introducing nitrogen for protection, performing grafting reaction under the action of an initiator, and taking out and drying after the reaction is finished. The invention adopts double bond coupling agent and maleic anhydride as modifier, introduces reactive functional groups on the surface of glass fiber, grafts low molecular weight PA6 on the surface of glass fiber by reaction extrusion technology, and finally melts and blends PA 6/glass fiber composite material with PA66, and the obtained PA66/GF composite material has good mechanical property.

Description

Glass fiber surface modification technology and application thereof in PA66
Technical Field
The invention relates to the technical field of high polymer materials and processing thereof, in particular to a glass fiber surface modification technology and application thereof in PA 66.
Background
Nylon 66, i.e. polyhexamethylene adipamide, for industrial short PA66, is a semi-crystalline thermoplastic polymer, which contains amide groups on its molecular main chain, can form hydrogen bonds, and has excellent mechanical properties, chemical stability, wear resistance and self-lubricating properties. However, the presence of amide groups in the PA66 molecular chain and low heat distortion temperature result in PA66 being prone to absorb water, severely affecting the mechanical properties, dimensional stability, low temperature impact resistance, etc. of PA 66. Glass Fiber (GF) is widely used as a reinforcing material, and is often used for improving the mechanical properties of polymer materials, and the strength and modulus of the glass fiber are ten times greater than those of nylon, so that the mechanical properties of PA66 can be greatly improved by adding the glass fiber into a PA66 matrix, and the dimensional stability is improved, so that the PA 66/glass fiber composite material is widely applied in the industrial field.
The Chinese patent application CN201810797506.8 discloses a glass fiber reinforced PA66 composite material and a preparation method thereof, wherein the interfacial binding force between the glass fiber and a matrix is enhanced by adding a lubricant, a coupling agent and a compatilizer, the problems of poor processing fluidity, high extrusion molding difficulty and the like of the glass fiber added into the PA66 matrix are solved, and meanwhile, the mechanical property of the composite material is improved. However, the compatibility of the glass fiber and the PA66 matrix is limited only by adding the coupling agent, the bond is easy to break under the action of melting heat and shearing force, and the interfacial bonding force between the glass fiber and the matrix is not obviously improved.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides a glass fiber surface modification technology and application thereof in a PA66 material with high mechanical property. The modification technology of the invention adopts a coupling agent containing double bonds and maleic anhydride as the modifier, introduces reactive functional groups on the surface of glass fiber, grafts low molecular weight PA6 on the surface of the glass fiber through a reaction extrusion technology, and finally melts and blends the PA 6/glass fiber composite material with PA66, thus the PA66/GF composite material has good mechanical properties.
In order to achieve the purpose of the invention, the glass fiber surface modification technology of the invention comprises the following steps: dissolving a double bond-containing coupling agent in a solvent 1 to prepare a solution, stirring and mixing glass fibers and the coupling agent solution, drying the mixture to obtain glass fibers with double bond functional groups on the surfaces, adding the glass fibers with the double bond functional groups on the surfaces, maleic anhydride and the solvent 2 into a reaction container, introducing nitrogen for protection, performing grafting reaction under the action of an initiator, and taking out and drying after the reaction is finished.
Further, in some embodiments of the present invention, the double bond coupling agent is selected from one or more of vinyltrimethoxysilane, vinyltriisopropoxysilane, vinyltriethoxysilane; preferably, the coupling agent is vinyltrimethoxysilane.
Further, in some embodiments of the invention, the solvent 1 is water, an alcohol, or a mixture of water and alcohol; preferably, the coupling agent comprises 5-15% by mass of the glass fiber, more preferably 5-10%.
Further, in some embodiments of the invention, the glass fibers are chopped glass fibers having a diameter of 3-10 μm and a length of 0.2-0.6mm.
Further, in some embodiments of the present invention, the mass ratio of the glass fiber to the maleic anhydride is 10 to 15:0.5-1.
Further, in some embodiments of the invention, the initiator is one or more of dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), azobisisobutyronitrile (AIBN); preferably, the initiator is DCP; preferably, the initiator is added in an amount of 0.1 to 0.5%.
Further, in some embodiments of the invention, the solvent 2 is one or more of chloroform, tetrahydrofuran, acetone, dioxane; preferably, the solvent 2 is acetone.
On the other hand, the invention also provides application of the glass fiber surface modification technology, wherein the application is that the surface modified glass fiber obtained by the glass fiber surface modification technology is reacted with low molecular weight nylon 6 (PA 6) to prepare low molecular weight PA 6/surface modified GF.
Further, in some embodiments of the invention, the low molecular weight PA 6/surface modified GF is prepared by: uniformly mixing low molecular weight PA6, surface modified glass fiber and antioxidant, then melting and extruding the mixture by a double screw extruder, carrying out chemical reaction on the terminal amino group in the low molecular weight PA6 and the acid anhydride group on the surface of the modified glass fiber in a molten state under the action of screw shearing and heat, and further extruding, cooling, drying and granulating to obtain the low molecular weight PA 6/surface modified GF.
Preferably, in some embodiments of the present invention, the antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 168, and antioxidant H3336.
Preferably, in some embodiments of the invention, the low molecular weight PA6 has a molecular weight of 10000-13000; more preferably, the low molecular weight PA6 has a molecular weight of 11000.
Preferably, in some embodiments of the invention, the mass ratio of the low molecular weight PA6, the surface modified glass fiber, and the antioxidant is 35-40:10-20:3; more preferably, the mass ratio of the low molecular weight PA6, the surface modified glass fiber and the antioxidant is 35-40:14-20:3.
Preferably, in some embodiments of the present invention, the twin screw extruder melt extrudes at a temperature of 220-275 ℃, a screw speed of 60-130rpm, and a vacuum of-0.06-0.03 MPa.
Preferably, in some embodiments of the invention, the twin screw extruder first zone temperature is 220-230 ℃; the temperature of the second area is 265-270 ℃; the temperature of the three regions and the six regions is 275 ℃; the temperature of the seventh area is 265 ℃; the temperature of the eighth zone is 255 ℃; the temperature of the nine areas is 230 ℃; the temperature of the ten areas is 255-265 ℃.
On the other hand, the invention also provides application of the low molecular weight PA 6/surface modified GF obtained by the preparation method, wherein the application is that the low molecular weight PA 6/surface modified GF is used for preparing the PA66 composite material with high mechanical property.
Further, in some embodiments of the present invention, the preparation method of the PA66 composite material with high mechanical properties is: uniformly mixing PA66, PA 6/surface modified GF and an antioxidant, then carrying out melt extrusion by a double screw extruder, further carrying out melt extrusion on the PA66 and the PA 6/surface modified GF under the action of screw shearing and heat, cooling, drying and granulating to obtain PA66/GF blended granules, namely the PA66 composite material with high mechanical property.
Preferably, in some embodiments of the invention, the mass ratio of PA66, PA 6/surface modified GF and antioxidant is 39-50:50-55:3.
Preferably, in some embodiments of the present invention, the twin screw extruder melt extrudes at a temperature of 220-275 ℃, a screw speed of 60-130rpm, and a vacuum of-0.06-0.03 MPa.
Preferably, in some embodiments of the invention, the twin screw extruder first zone temperature is 220-230 ℃; the temperature of the second area is 265-270 ℃; the temperature of the three regions and the six regions is 275 ℃; the temperature of the seventh area is 265 ℃; the temperature of the eighth zone is 255 ℃; the temperature of the nine areas is 230 ℃; the temperature of the ten areas is 255-265 ℃.
Aiming at the defect of low mechanical property caused by uneven distribution of glass fibers in the current PA66 composite material, the invention adopts a surface grafting method to introduce reactive functional groups on the glass fibers, and simultaneously utilizes a reaction extrusion technology to react low molecular weight PA6 with the functional groups on the glass fibers, thereby further improving the interfacial binding force between the glass fibers and the PA66 matrix, and the glass fibers are uniformly dispersed in the PA66 matrix, so that the high mechanical property of the PA66 composite material is realized.
Drawings
FIG. 1 is a schematic representation of the glass fiber modification of the present invention;
FIG. 2 is a glass fiber surface grafted low molecular weight PA6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The PA66 composite material with high mechanical property obtained by the method is dried to constant weight at the temperature of 85-95 ℃, and then standard sample bars for evaluating the mechanical property of the PA66/GF composite material are obtained by injection molding. The injection molding processing conditions are as follows: the temperature interval of each heating section is 260-280 ℃; the injection molding pressure is 80-120MPa; the pressure maintaining pressure is 40-60MPa; the dwell time is 20-30s. Preferably, the PA66 composite material with high mechanical property is obtained in the embodiment of the invention, is dried to constant weight at 90 ℃, and then the blended granules are put into an injection molding machine for injection molding at 270 ℃ and 100MPa of injection pressure and 25s of dwell time.
Example 1
The PA 66/low molecular weight PA 6/modified glass fiber high-performance composite material comprises the following raw materials in parts by weight: 50 parts of PA66 granules, 40 parts of low molecular weight PA6 (11000), 15 parts of chopped glass fibers, 1.5 parts of vinyl trimethoxy silane, 0.5 part of maleic anhydride and 3 parts of antioxidant (antioxidant 1010 and antioxidant 1098 in a mass ratio of 1:1), wherein the total mass of the raw materials is 2Kg.
The preparation process of the material is as follows:
(1) Dissolving vinyl trimethoxy silane in ethanol water solution to prepare a solution, and placing glass fiber and vinyl trimethoxy silane solution (accounting for 10wt% of the glass fiber) in a high-speed stirrer to stir for 3min; then it was placed in an oven at 120 ℃ for drying.
(2) Adding the glass fiber treated by the coupling agent obtained in the step (1), maleic anhydride and acetone into a three-mouth bottle, introducing nitrogen for protection, performing grafting reaction on the glass fiber and the maleic anhydride under the action of dicumyl peroxide, taking out the glass fiber after the reaction is finished, and putting the glass fiber into an oven for drying.
(3) And (3) uniformly mixing the modified glass fiber obtained in the step (2), low molecular weight PA6 and an antioxidant, adding the mixture into a double-screw extruder, extruding, cooling, drying and granulating the mixture at the processing temperature of 260-280 ℃ and the screw rotation speed of 120rpm to obtain the low molecular weight PA 6/surface modified GF composite material.
(4) Uniformly mixing the low molecular weight PA 6/surface modified GF composite material obtained in the step (3), PA66 and an antioxidant, adding the mixture into a double-screw extruder, extruding the mixture at a processing temperature of 260-280 ℃ and a screw rotating speed of 120rpm, cooling, drying and granulating the mixture to obtain the PA66 composite material with high mechanical property.
(5) And (3) putting the PA66 composite material with high mechanical property obtained in the step (4) into a blast oven to be dried to constant weight at the temperature of 90 ℃.
(6) And (3) adding the dried high mechanical property PA66 composite material obtained in the step (5) into an injection molding machine, and performing injection molding at 260-280 ℃ to obtain a PA66/GF composite material test spline.
Example 2
The PA 66/low molecular weight PA 6/modified glass fiber high-performance composite material comprises the following raw materials in parts by weight: 39 parts of PA66 granules, 40 parts of low molecular weight PA6 (11000), 15 parts of chopped glass fibers, 1.5 parts of vinyl trimethoxy silane, 1.5 parts of maleic anhydride and 3 parts of antioxidant (antioxidant 1010 and antioxidant 1098 in a mass ratio of 1:1), wherein the total mass of the raw materials is 2Kg.
The preparation process of the material is as follows:
(1) Dissolving vinyl trimethoxy silane in ethanol water solution to prepare a solution, and placing glass fiber and vinyl trimethoxy silane solution (accounting for 10wt% of the glass fiber) in a high-speed stirrer to stir for 3min; then it was placed in an oven at 120 ℃ for drying.
(2) Adding the glass fiber treated by the coupling agent obtained in the step (1), maleic anhydride and acetone into a three-mouth bottle, introducing nitrogen for protection, performing grafting reaction on the glass fiber and the maleic anhydride under the action of dicumyl peroxide, taking out the glass fiber after the reaction is finished, and putting the glass fiber into an oven for drying.
(3) And (3) uniformly mixing the modified glass fiber obtained in the step (2), low molecular weight PA6 and an antioxidant, adding the mixture into a double-screw extruder, extruding, cooling, drying and granulating the mixture at the processing temperature of 260-280 ℃ and the screw rotation speed of 120rpm to obtain the low molecular weight PA 6/surface modified GF composite material.
(4) Uniformly mixing the low molecular weight PA 6/surface modified GF composite material obtained in the step (3), PA66 and an antioxidant, adding the mixture into a double-screw extruder, extruding the mixture at a processing temperature of 260-280 ℃ and a screw rotating speed of 120rpm, cooling, drying and granulating the mixture to obtain the PA66 composite material with high mechanical property.
(5) And (3) putting the PA66 composite material with high mechanical property obtained in the step (4) into a blast oven to be dried to constant weight at the temperature of 90 ℃.
(6) And (3) adding the dried high mechanical property PA66 composite material obtained in the step (5) into an injection molding machine, and performing injection molding at 260-280 ℃ to obtain a PA66/GF composite material test spline.
Example 3
The PA 66/low molecular weight PA 6/modified glass fiber high-performance composite material comprises the following raw materials in parts by weight: 45 parts of PA66 granules, 35 parts of low molecular weight PA6 (11000), 15 parts of chopped glass fibers, 1.5 parts of vinyl trimethoxy silane, 0.5 part of maleic anhydride and 3 parts of antioxidant (antioxidant 1010 and antioxidant 1098 in a mass ratio of 1:1), wherein the total mass of the raw materials is 2Kg.
The preparation process of the material is as follows:
(1) Dissolving vinyl trimethoxy silane in ethanol water solution to prepare a solution, and placing glass fiber and vinyl trimethoxy silane solution (accounting for 10wt% of the glass fiber) in a high-speed stirrer to stir for 3min; then it was placed in an oven at 120 ℃ for drying.
(2) Adding the glass fiber treated by the coupling agent obtained in the step (1), maleic anhydride and acetone into a three-mouth bottle, introducing nitrogen for protection, performing grafting reaction on the glass fiber and the maleic anhydride under the action of dicumyl peroxide, taking out the glass fiber after the reaction is finished, and putting the glass fiber into an oven for drying.
(3) And (3) uniformly mixing the modified glass fiber obtained in the step (2), low molecular weight PA6 and an antioxidant, adding the mixture into a double-screw extruder, extruding, cooling, drying and granulating the mixture at the processing temperature of 260-280 ℃ and the screw rotation speed of 120rpm to obtain the low molecular weight PA 6/surface modified GF composite material.
(4) Uniformly mixing the low molecular weight PA 6/surface modified GF composite material obtained in the step (3), PA66 and an antioxidant, adding the mixture into a double-screw extruder, extruding the mixture at a processing temperature of 260-280 ℃ and a screw rotating speed of 120rpm, cooling, drying and granulating the mixture to obtain the PA66 composite material with high mechanical property.
(5) And (3) putting the PA66 composite material with high mechanical property obtained in the step (4) into a blast oven to be dried to constant weight at the temperature of 90 ℃.
(6) And (3) adding the dried high mechanical property PA66 composite material obtained in the step (5) into an injection molding machine, and performing injection molding at 260-280 ℃ to obtain a PA66/GF composite material test spline.
Example 4
The PA 66/low molecular weight PA 6/modified glass fiber high-performance composite material comprises the following raw materials in parts by weight: 45.5 parts of PA66 granules, 40 parts of low molecular weight PA6 (11000), 10 parts of chopped glass fibers, 1 part of vinyltrimethoxysilane, 0.5 part of maleic anhydride and 3 parts of antioxidant (the mass ratio of antioxidant 1010 to antioxidant 1098 is 1:1), wherein the total mass of the raw materials is 2Kg.
The preparation process of the material is as follows:
(1) Dissolving vinyl trimethoxy silane in ethanol water solution to prepare a solution, and placing glass fiber and vinyl trimethoxy silane (accounting for 10wt% of the glass fiber) solution in a high-speed stirrer to stir for 3min; then it was placed in an oven at 120 ℃ for drying.
(2) Adding the glass fiber treated by the coupling agent obtained in the step (1), maleic anhydride and acetone into a three-mouth bottle, introducing nitrogen for protection, performing grafting reaction on the glass fiber and the maleic anhydride under the action of dicumyl peroxide, taking out the glass fiber after the reaction is finished, and putting the glass fiber into an oven for drying.
(3) And (3) uniformly mixing the modified glass fiber obtained in the step (2), low molecular weight PA6 and an antioxidant, adding the mixture into a double-screw extruder, extruding, cooling, drying and granulating the mixture at the processing temperature of 260-280 ℃ and the screw rotation speed of 120rpm to obtain the low molecular weight PA 6/surface modified GF composite material.
(4) Uniformly mixing the low molecular weight PA 6/surface modified GF composite material obtained in the step (3), PA66 and an antioxidant, adding the mixture into a double-screw extruder, extruding the mixture at a processing temperature of 260-280 ℃ and a screw rotating speed of 120rpm, cooling, drying and granulating the mixture to obtain the PA66 composite material with high mechanical property.
(5) And (3) putting the PA66 composite material with high mechanical property obtained in the step (4) into a blast oven to be dried to constant weight at the temperature of 90 ℃.
(6) And (3) adding the dried high mechanical property PA66 composite material obtained in the step (5) into an injection molding machine, and performing injection molding at 260-280 ℃ to obtain a PA66/GF composite material test spline.
Example 5
The PA 66/low molecular weight PA 6/modified glass fiber high-performance composite material comprises the following raw materials in parts by weight: 40.75 parts of PA66 granules, 40 parts of low molecular weight PA6 (11000), 15 parts of chopped glass fibers, 0.75 part of vinyltrimethoxysilane, 0.5 part of maleic anhydride and 3 parts of antioxidant (the mass ratio of antioxidant 1010 to antioxidant 1098 is 1:1), wherein the total mass of the raw materials is 2Kg.
The preparation process of the material is as follows:
(1) Dissolving vinyl trimethoxy silane in ethanol water solution to prepare a solution, and placing glass fiber and vinyl trimethoxy silane (accounting for 5wt% of the glass fiber) solution in a high-speed stirrer to stir for 3min; then it was placed in an oven at 120 ℃ for drying.
(2) Adding the glass fiber treated by the coupling agent obtained in the step (1), maleic anhydride and acetone into a three-mouth bottle, introducing nitrogen for protection, performing grafting reaction on the glass fiber and the maleic anhydride under the action of dicumyl peroxide, taking out the glass fiber after the reaction is finished, and putting the glass fiber into an oven for drying.
(3) And (3) uniformly mixing the modified glass fiber obtained in the step (2), low molecular weight PA6 and an antioxidant, adding the mixture into a double-screw extruder, extruding, cooling, drying and granulating the mixture at the processing temperature of 260-280 ℃ and the screw rotation speed of 120rpm to obtain the low molecular weight PA 6/surface modified GF composite material.
(4) Uniformly mixing the low molecular weight PA 6/surface modified GF composite material obtained in the step (3), PA66 and an antioxidant, adding the mixture into a double-screw extruder, extruding the mixture at a processing temperature of 260-280 ℃ and a screw rotating speed of 120rpm, cooling, drying and granulating the mixture to obtain the PA66 composite material with high mechanical property.
(5) And (3) putting the PA66 composite material with high mechanical property obtained in the step (4) into a blast oven to be dried to constant weight at the temperature of 90 ℃.
(6) And (3) adding the dried high mechanical property PA66 composite material obtained in the step (5) into an injection molding machine, and performing injection molding at 260-280 ℃ to obtain a PA66/GF composite material test spline.
Comparative example 1
The PA 66/low molecular weight PA 6/modified glass fiber high-performance composite material comprises the following raw materials in parts by weight: 42 parts of PA66 granules, 40 parts of low molecular weight PA6 (11000), 15 parts of chopped glass fibers, 3 parts of antioxidant (antioxidant 1010 and antioxidant 1098 in a mass ratio of 1:1), and the total mass of the raw materials is 2Kg.
The preparation process of the material is as follows:
(1) Uniformly mixing PA66, chopped glass fibers, PA6 and an antioxidant, adding the mixture into a double-screw extruder, extruding the mixture at a processing temperature of 260-280 ℃ and a screw rotating speed of 120rpm, cooling, drying and granulating the mixture to obtain PA66/GF blend granules.
(2) And (3) putting the PA66/GF blend granules obtained in the step (1) into a blast oven to be dried to constant weight at the temperature of 90 ℃.
(3) And (3) adding the dried PA66/GF blending granules obtained in the step (2) into an injection molding machine, and performing injection molding at 260-280 ℃ to obtain the PA66/GF composite material.
Comparative example 2
The PA 66/glass fiber composite material comprises the following raw materials in parts by weight: 80 parts of PA66 granules, 15 parts of chopped glass fibers, 1.5 parts of vinyl trimethoxy silane, 0.5 part of maleic anhydride and 3 parts of antioxidant (the mass ratio of antioxidant 1010 to antioxidant 1098 is 1:1), wherein the total mass of the raw materials is 2kg.
The preparation process of the material is as follows:
(1) Dissolving a coupling agent in an ethanol water solution to prepare a coupling agent solution, and placing glass fiber and the coupling agent solution (accounting for 10wt% of the glass fiber) in a high-speed stirrer to stir for 3min;
(2) Placing the modified glass fiber obtained in the step (1) in a baking oven at 120 ℃ for 3 hours to obtain a coupling agent modified glass fiber;
(3) And (3) uniformly mixing the modified glass fiber obtained in the step (2), maleic anhydride, PA66 and an antioxidant, adding the mixture into a double-screw extruder, extruding the mixture at a processing temperature of 260-280 ℃ and a screw rotating speed of 120rpm, cooling, drying and granulating the mixture to obtain PA66/GF blend granules.
(4) And (3) putting the PA66/GF blend granules obtained in the step (3) into a blast oven to be dried to constant weight at the temperature of 90 ℃.
(5) And (3) adding the dried PA66/GF blending granules obtained in the step (4) into an injection molding machine, and performing injection molding at 260-280 ℃ to obtain the PA66/GF composite material.
Performance test and results
The mechanical property test is carried out on the injection molded PA66/GF composite material, and the specific test method is as follows:
tensile properties: according to GB/T1040 test, the sample size is 150mm multiplied by 10mm multiplied by 4mm, and the stretching speed is 50mm/min;
bending properties: the sample size was 80mm by 10mm by 4mm and the speed was 2mm/min according to GB/T9341 test;
impact properties: the sample size was 80mm by 10mm by 4mm as measured in GB/T1043.
TABLE 1 summary of data on mechanical properties of PA66/GF composite materials
As can be seen from the above table, compared with comparative examples 1-2, the mechanical properties of the PA66/GF composite materials provided in examples 1-3 are significantly improved, because the glass fibers are modified by only adding the coupling agent or only adding PA6 compared with the modification by using the coupling agent plus low molecular weight PA6, the interfacial bonding force between the glass fibers and the PA66 matrix is further improved, and the problem that the mechanical properties of the composite materials are not high due to uneven dispersion of the glass fibers is solved. Comparison of example 1 with example 4 demonstrates that the use of increased glass fiber content is beneficial to improving the mechanical properties of the PA66/GF composite material. Comparison of example 1 and example 5 shows that the optimum ratio of coupling agent content in PA66/GF is 10wt% and that GF is sufficiently modified by the coupling agent.
It will be readily appreciated by those skilled in the art that the foregoing is merely illustrative of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements or the like which fall within the spirit and principles of the present invention are intended to be included within the scope of the present invention.

Claims (12)

1. The application of the low molecular weight PA 6/surface modified glass fiber prepared by the preparation method of the low molecular weight PA 6/surface modified glass fiber is characterized in that the application is that the low molecular weight PA 6/surface modified glass fiber is used for preparing a PA66 composite material with high mechanical property; the modification method of the surface modified glass fiber comprises the following steps: dissolving a double bond-containing coupling agent in a solvent 1 to prepare a solution, stirring and mixing glass fibers and the coupling agent solution, then drying the mixture to obtain glass fibers with double bond functional groups on the surfaces, adding the glass fibers with the double bond functional groups on the surfaces, maleic anhydride and the solvent 2 into a reaction container, introducing nitrogen for protection, performing grafting reaction under the action of an initiator, and taking out and drying after the reaction is finished;
the obtained surface modified glass fiber reacts with low molecular weight PA6 to prepare low molecular weight PA 6/surface modified glass fiber;
uniformly mixing low molecular weight PA6, surface modified glass fiber and an antioxidant, then carrying out melt extrusion by a double screw extruder, carrying out chemical reaction on an amino end group in the low molecular weight PA6 and an anhydride group on the surface of the modified glass fiber in a molten state under the action of screw shearing and heat, and further carrying out extrusion, cooling, drying and granulating to obtain the low molecular weight PA 6/surface modified glass fiber; the antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 168 and antioxidant H3336; the molecular weight of the low molecular weight PA6 is 10000-13000; the mass ratio of the low molecular weight PA6 to the surface modified glass fiber to the antioxidant is 35-40:10-20:3; the temperature of the melt extrusion of the double-screw extruder is 220-275 ℃, the screw rotating speed is 60-130rpm, and the vacuum degree is-0.06-0.03 MPa; the temperature of a first area of the twin-screw extruder is 220-230 ℃; the temperature of the second area is 265-270 ℃; the temperature of the three regions and the six regions is 275 ℃; the temperature of the seventh area is 265 ℃; the temperature of the eighth zone is 255 ℃; the temperature of the nine areas is 230 ℃; the temperature of the ten areas is 255-265 ℃.
2. The use of a low molecular weight PA 6/surface modified glass fiber as defined in claim 1, wherein said double bond coupling agent is selected from the group consisting of vinyltrimethoxysilane, vinyltriisopropoxysilane, and vinyltriethoxysilane.
3. The use of a low molecular weight PA 6/surface modified glass fiber as defined in claim 1, wherein said coupling agent is vinyltrimethoxysilane.
4. The use of low molecular weight PA 6/surface modified glass fiber made by the process for the preparation of low molecular weight PA 6/surface modified glass fiber according to claim 1, wherein the solvent 1 is water, alcohol or a mixture of water and alcohol; the coupling agent accounts for 5-15% of the mass of the glass fiber; the glass fiber is chopped glass fiber, the diameter is 3-10 mu m, and the length is 0.2-0.6mm; the mass ratio of the glass fiber to the maleic anhydride is 10-15:0.5-1.
5. The use of low molecular weight PA 6/surface modified glass fiber as defined in claim 1, wherein said initiator is one or more of dicumyl peroxide, dibenzoyl peroxide, azobisisobutyronitrile.
6. The use of low molecular weight PA 6/surface modified glass fiber made by the process for the preparation of low molecular weight PA 6/surface modified glass fiber as claimed in claim 1, wherein the initiator is dicumyl peroxide; the addition amount of the initiator is 0.1-0.5%.
7. The use of low molecular weight PA 6/surface modified glass fiber as defined in claim 1, wherein the solvent 2 is one or more of chloroform, tetrahydrofuran, acetone, dioxane.
8. The use of low molecular weight PA 6/surface modified glass fiber as defined in claim 1, wherein said solvent 2 is acetone.
9. The use of a low molecular weight PA 6/surface modified glass fiber as defined in claim 1, wherein the low molecular weight PA6 has a molecular weight of 11000.
10. The use of low molecular weight PA 6/surface modified glass fiber as defined in claim 1, wherein the mass ratio of low molecular weight PA6, surface modified glass fiber and antioxidant is from 35-40:14 to 20:3.
11. The use of the low molecular weight PA 6/surface modified glass fiber produced by the process for producing low molecular weight PA 6/surface modified glass fiber according to claim 1, wherein the process for producing the high mechanical PA66 composite material is: uniformly mixing PA66, low molecular weight PA 6/surface modified glass fiber and antioxidant, then carrying out melt extrusion by a double screw extruder, further carrying out melt extrusion on the PA66 and the low molecular weight PA 6/surface modified glass fiber under the action of screw shearing and heat, and cooling, drying and granulating to obtain PA66/GF blend granules, namely the PA66 composite material with high mechanical property.
12. The use of low molecular weight PA 6/surface modified glass fiber as defined in claim 11, wherein the mass ratio of PA66, low molecular weight PA 6/surface modified glass fiber and antioxidant is 39-50:50-55:3; the temperature of the melt extrusion of the double-screw extruder is 220-275 ℃, the screw rotating speed is 60-130rpm, and the vacuum degree is-0.06-0.03 MPa; the temperature of a first area of the twin-screw extruder is 220-230 ℃; the temperature of the second area is 265-270 ℃; the temperature of the three regions and the six regions is 275 ℃; the temperature of the seventh area is 265 ℃; the temperature of the eighth zone is 255 ℃; the temperature of the nine areas is 230 ℃; the temperature of the ten areas is 255-265 ℃.
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