CN114891249A - Preparation method of glass fiber reinforced epoxy resin composite material - Google Patents
Preparation method of glass fiber reinforced epoxy resin composite material Download PDFInfo
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- CN114891249A CN114891249A CN202210496482.9A CN202210496482A CN114891249A CN 114891249 A CN114891249 A CN 114891249A CN 202210496482 A CN202210496482 A CN 202210496482A CN 114891249 A CN114891249 A CN 114891249A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 106
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 19
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- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
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- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical group C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 23
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical group [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 11
- 150000002148 esters Chemical group 0.000 claims description 11
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000007519 polyprotic acids Polymers 0.000 claims description 4
- 150000002894 organic compounds Chemical group 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
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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
- C08J5/0405—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
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention provides a preparation method of a glass fiber reinforced epoxy resin composite material, which comprises the following steps: mixing an epoxy resin monomer, an acid curing agent, an ester exchange catalyst and chopped glass fibers to obtain a mixture; and pouring the mixture into polymer processing equipment, and carrying out dynamic vulcanization under the action of strong shearing to obtain the glass fiber reinforced epoxy resin composite material. The invention utilizes the strong shearing action which is continuously existed in the dynamic crosslinking process, realizes the good dispersion of the glass fiber in the crosslinking epoxy resin under the condition of not carrying out surface modification on the glass fiber, and the well-dispersed glass fiber can be locked in the matrix along with the crosslinking of the polymer matrix along with the progress of dynamic vulcanization, thereby realizing the good and stable dispersion of the glass fiber in the epoxy resin matrix. The invention realizes the high-efficiency, low-cost and rapid preparation of the glass fiber reinforced epoxy resin composite material, and has important significance for large-scale production and industrial application.
Description
Technical Field
The invention relates to the technical field of epoxy resin materials, in particular to a preparation method of a glass fiber reinforced epoxy resin composite material.
Background
One of the most important and most widely used thermosets is epoxy resins, which have a market share of about 70% in the global thermoset market, whose permanently crosslinked structure imparts to the epoxy resins many superior properties, including excellent mechanical properties, chemical resistance, heat resistance, and dimensional stability. This makes it irreplaceable in a variety of applications such as sealants, coatings, adhesives, electronic devices, and high performance composites. In order to further improve the mechanical property and the thermal property of the epoxy resin, various inorganic materials are usually filled in the epoxy resin to prepare the epoxy resin composite material, so that on one hand, the mechanical property (modulus, strength and fracture toughness) and the thermal stability of the epoxy resin can be improved, and on the other hand, the cost can be obviously reduced. The glass fiber is a high-performance inorganic material with excellent mechanical property, corrosion resistance, high temperature resistance and good insulativity. The glass fiber composite material (which can be called glass fiber reinforced epoxy resin composite material) formed by compounding the glass fiber composite material with epoxy resin has excellent mechanical property and thermal stability, and is widely applied to various fields of national economy. Glass fiber composites account for over 70% of the total composite market. However, the permanently crosslinked structure also presents serious problems for epoxy/fiberglass composites, which once cured cannot be reprocessed, molded or heat recovered, leading to serious environmental problems and waste of resources through the life of the epoxy.
In addition, the dispersion effect of the chopped glass fibers in the epoxy resin directly affects the mechanical properties of the composite material, and in order to achieve a good reinforcing effect of the chopped glass fibers on the epoxy resin, the glass fibers need to be uniformly dispersed in the epoxy resin matrix. However, since the chopped glass fiber is an inorganic material and has poor interface compatibility with the organic polymer epoxy resin, the chopped glass fiber is easy to form spontaneous agglomeration during the curing process of the epoxy resin. Coupled with the strong interaction between the chopped glass fibers, it is difficult to avoid agglomeration of the untreated chopped glass fibers in the thermosetting epoxy resin matrix. At present, the surface modification of glass fiber is usually adopted, for example, after the glass fiber is treated by a coupling agent, the bending strength and the notch impact strength of the prepared epoxy resin composite material are greatly improved (Zhang hong Jun, Xiaodao Dong, Daihong, etc., the synthesis of a block copolymerization coupling agent and the influence thereof on the performance of the glass fiber epoxy composite material [ J ] composite material science and engineering, 2005, 03: 30-34). Chinese patent CN 106739394A reports that the mechanical property of the prepared epoxy resin/glass fiber composite material is obviously improved by modifying the glass fiber with a surface modifier.
The preparation method of the epoxy resin/chopped glass fiber composite material adopts a traditional static curing method, namely, the chopped glass fiber is modified, the curing agent and the modified glass fiber are added into the epoxy resin monomer, and after the epoxy resin monomer and the modified glass fiber are uniformly mixed, the epoxy resin/chopped glass fiber composite material is obtained through static curing reaction under a certain temperature condition. However, at present, the preparation process of the chopped glass fiber reinforced epoxy resin composite material is complicated in steps, low in production efficiency and high in preparation cost, and a large amount of organic waste liquid is generated in the preparation process. In addition, chemical reagents and organic solvents for modification also cause environmental pollution, and are not favorable for large-scale industrial production. Therefore, the glass fiber reinforced epoxy resin composite material meets the good reinforcing effect, and simultaneously, a preparation method which is green, environment-friendly, simple, convenient and fast and does not need to carry out special treatment on glass fibers is urgently needed.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a glass fiber reinforced epoxy resin composite material, and the method can obtain a well-reinforced epoxy resin composite material, is green, environment-friendly, simple, convenient and fast, and is beneficial to large-scale industrial production.
The invention provides a preparation method of a glass fiber reinforced epoxy resin composite material, which comprises the following steps: mixing an epoxy resin monomer, an acid curing agent, an ester exchange catalyst and chopped glass fibers to obtain a mixture; and pouring the mixture into polymer processing equipment, and carrying out dynamic vulcanization under the action of strong shearing to obtain the glass fiber reinforced epoxy resin composite material.
Preferably, the epoxy resin monomer is an organic compound having two or more epoxy groups in a molecule, such as a bisphenol a type epoxy resin monomer. Further preferably, the epoxy resin monomer is bisphenol A diglycidyl ether (DGEBA, molecular weight: 348).
Preferably, the acid curing agent is one or more of polyanhydride and polyacid, including but not limited to glutaric anhydride, sebacic acid; wherein the molar ratio of the carboxyl to the epoxy resin monomer is 1: 1.
Preferably, the dynamic vulcanization is carried out at a rotation speed of 50-80 rpm and a temperature of 160-200 ℃.
Preferably, the decomposition temperature of the transesterification catalyst is higher than 160 ℃. Further preferably, the transesterification catalyst is zinc acetylacetonate. Preferably, the molar number of the ester exchange catalyst is 5 to 20 percent of the molar number of the epoxy group of the epoxy resin monomer.
Preferably, the diameter of the chopped glass fiber is 0.04-19 μm, and the length of the chopped glass fiber can be 2-5000 μm; the mass percentage of the chopped glass fiber is between 0 and 50 percent.
Preferably, the polymer processing equipment is one of an internal mixer, a single screw extruder and a twin screw extruder.
For epoxy resins, the introduction of dynamic covalent bonds into their structure is an effective method for imparting ductility and hot workability to epoxy resins, since the exchange reaction of dynamic covalent bonds proceeds by network topological rearrangement under external stimuli (e.g., heat and ultraviolet light), thereby imparting plasticity to epoxy resins. Polymer networks containing dynamic cross-links are called Covalent Adaptive Networks (CAN), and are generally classified into dissociative and bound CANs according to the exchange reaction mechanism of different dynamic Covalent bonds. The bonded CAN is also called glass-like polymers (vitomers), which are bonded by an exchange reactionIn the process of configuration and rearrangement, the topological structure still maintains a complete network structure. The first epoxy-based hydroxyl-transesterification glass-like polymer was reported by Leibler in 2011 (Damien Montarnal M C,
Tournilhac，Ludwik Leibler.Silica-Like Malleable Materials from Permanent Organic Networks[J]SCIENCE, 2011, 334: 965-967.). The advent of glass-like polymers has made it possible to process crosslinked network polymers like linear or branched thermoplastic polymers, which provides an efficient method for recycling thermosets such as epoxy resins.
Although the epoxy glass polymer is introduced to realize the recycling of epoxy resin, the preparation method of the epoxy glass polymer/chopped glass fiber composite material still adopts the traditional static curing method, and the problems of secondary agglomeration of glass fiber, high cost for carrying out chemical modification on the glass fiber, complex steps and the like exist in the traditional static curing process.
Aiming at the problem of preparing the chopped glass fiber reinforced epoxy resin composite material, the process improvement of the invention is as follows: the chopped glass fiber, epoxy monomer, acid curing agent and ester exchange catalyst are added into polymer processing equipment (internal mixer and twin-screw extruder) and dynamically vulcanized under the action of a shearing field. The invention innovatively combines a dynamic crosslinking technology, epoxy resin, glass fiber and the like, utilizes the strong shearing action continuously existing in the dynamic crosslinking process, realizes the good dispersion of the glass fiber in the crosslinked epoxy resin under the condition of not carrying out surface modification on the glass fiber, and locks the well-dispersed glass fiber in a matrix along with the crosslinking of a polymer matrix along with the dynamic vulcanization, thereby avoiding the secondary agglomeration of the glass fiber and realizing the good and stable dispersion of the glass fiber in the epoxy resin matrix. The method can realize the efficient, low-cost and rapid preparation of the glass fiber reinforced epoxy resin composite material, and has important significance for large-scale production and industrial application thereof.
Drawings
FIG. 1 is a scanning electron micrograph of a reinforced composite prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a preparation method of a glass fiber reinforced epoxy resin composite material, which comprises the following steps:
mixing an epoxy resin monomer, an acid curing agent, an ester exchange catalyst and chopped glass fibers to obtain a mixture;
and pouring the mixture into polymer processing equipment, and carrying out dynamic vulcanization under the action of strong shearing to obtain the glass fiber reinforced epoxy resin composite material.
The preparation method of the chopped glass fiber reinforced epoxy resin composite material provided by the invention is green, environment-friendly, simple and convenient, does not need to specially treat glass fibers, has good material performance and high production efficiency, and is beneficial to large-scale industrial production.
The epoxy resin monomer, the acid curing agent, the ester exchange catalyst and the chopped glass fiber are preferably weighed respectively at normal temperature, and the weighed materials are mixed and stirred to obtain a uniform mixture. The normal temperature is a temperature condition well known to those skilled in the art, such as a room temperature of 10-30 ℃.
In the embodiment of the present invention, the epoxy resin monomer raw material has a multifunctional group, that is, includes an organic compound having two or more epoxy groups in a molecule, preferably a bisphenol a epoxy resin monomer, more preferably bisphenol a diglycidyl ether (DGEBA), and is widely used.
The structural formula of bisphenol a diglycidyl ether is as follows, and its molecular weight: 348, it is commercially available;
the curing agent selected by the embodiment of the invention is one or a mixture of acid curing agents of polybasic acid anhydride and polybasic acid, such as glutaric anhydride and/or sebacic acid; wherein the molar ratio of the carboxyl to the epoxy of the epoxy resin monomer can be kept at 1: 1.
In the embodiment of the invention, an ester exchange catalyst is added to participate in dynamic vulcanization; the ester exchange catalyst can be any ester exchange catalyst which does not decompose under the conditions of 160-220 ℃, and the adding mole number of the ester exchange catalyst is 5-20% of the mole number of epoxy groups of epoxy resin monomers. Preferably, the transesterification catalyst is zinc acetylacetonate.
Further, in embodiments of the present invention, the chopped glass fibers may have a diameter of 0.04 to 19 μm and a length of between 2 to 5000 μm; the mass percentage of the chopped glass fiber is between 0 and 50wt percent. The glass fiber addition is different from 0 and the mass percent can be expressed correspondingly as wt%.
The glass fiber reinforced epoxy resin composite material provided by the embodiment of the invention is prepared by mixing an epoxy resin monomer, an acid curing agent, an ester exchange catalyst and chopped glass fibers and then performing dynamic vulcanization, wherein the chopped glass fibers are glass fibers which are not subjected to any chemical treatment, and the dynamic vulcanization process is performed on traditional polymer processing equipment such as thermoplastic resin.
That is, in the embodiment of the present invention, the mixture obtained by the above mixing is poured into a polymer processing device, and dynamic vulcanization is preferably performed at a rotation speed of 50-80 rpm and a temperature of 160-200 ℃, wherein the time can be 10-40 minutes, so as to obtain the chopped glass fiber reinforced epoxy resin composite material.
Wherein, the polymer processing equipment, namely the dynamic vulcanization equipment, can select one of an internal mixer, a single-screw extruder and a double-screw extruder. The temperature of the dynamic vulcanization can be 160 ℃, 170 ℃, 180 ℃, 185 ℃ and the like; the glass fiber loading in the resulting composite is preferably 5-50 wt%.
The embodiment of the invention tests the mechanical property, the thermal stability and the like of the obtained composite material, and the test method comprises the following specific steps:
1. gel content test
The gel fraction of the samples was measured by the solvent immersion method. The sample was immersed in chloroform at room temperature for 3 days to dissolve the uncured part of the product, and the cured part was collected by filtration and then vacuum-dried at 80 ℃ for 24 hours. Gel fraction (G) f ) Calculated by the following formula:
G f (％)＝W 2 /W 1 ×100％；
wherein W 2 And W 1 Respectively, the dry weight of the insoluble portion of the sample and the initial weight of the original product before immersion in chloroform.
2. Mechanical Property test
The prepared epoxy resin/glass fiber composite material sample is molded for 10 minutes at 180 ℃ under 20MPa, and a dumbbell-shaped sample (width: 4mm, thickness: 0.5mm) is cut out after cooling. Tensile experiments were conducted using an MTS E44 universal mechanical testing machine in tensile mode at a crosshead speed of 10 mm/min. For all tests, five samples were tested for each polymer and the average results were collected, with the tests being performed at room temperature (25 ℃).
3. Scanning electron microscope
Scanning electron microscope: scanning Electron Microscope (SEM) was used to observe the distribution of glass fiber composite material in the matrix by using a Scanning Electron Microscope, model S-4800, Hitachi, Japan, wherein the sample was quenched with liquid nitrogen and then the cross section of the sample was subjected to metal spraying treatment at an accelerating voltage of 20 kV.
4. Thermal stability test
Carrying out thermal stability performance test on the chopped glass fiber reinforced composite material sample by adopting a NETZSCH TG209F1 thermogravimetric analyzer; and (3) testing conditions are as follows: under nitrogen atmosphere, the heating rate is 10 ℃/min, the gas flow rate is 50mL/min, and the temperature range is from room temperature to 800 ℃.
The test result shows that the glass fiber reinforced epoxy resin composite material prepared by the embodiment of the invention meets the good reinforcing effect. Meanwhile, the method is environment-friendly, simple, convenient and low in cost.
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention. The following examples of the invention employ the following raw material sources:
bisphenol a diglycidyl ether (dow chemical limited), sebacic acid (mclin reagent limited), zinc acetylacetonate (shanghai meirill reagent limited), glutaric anhydride (alatin reagent limited), and chopped glass fiber (chongqing international composite material limited, brand: 3014B). Wherein, the molar ratio of carboxyl to epoxy in the raw material system is kept at 1: 1.
In addition, the test method of the embodiment of the invention is as described above.
Example 1:
under the condition of room temperature, respectively weighing 17.40g of bisphenol A diglycidyl ether (DGEBA, molecular weight: 348), 10.11g of sebacic acid, 1.32g of zinc acetylacetonate and 1.44g of glass fiber, uniformly mixing, pouring into an internal mixer, dynamically vulcanizing at 180 ℃ under the condition of 80 revolutions per minute, and after 20 minutes, finishing the reaction to obtain the epoxy resin composite material with the glass fiber filling amount of 5 wt%.
Example 2:
1740g of bisphenol A diglycidyl ether (DGEBA, molecular weight: 348), 1011g of sebacic acid, 132g of zinc acetylacetonate and 144g of glass fiber are respectively weighed at room temperature, uniformly mixed, poured into a double-screw extruder, dynamically vulcanized for 40 minutes at 180 ℃ and 80 revolutions per minute and extruded to obtain the epoxy resin composite material with the glass fiber filling amount of 5 wt%.
Example 3:
under the condition of room temperature, respectively weighing 17.40g of bisphenol A diglycidyl ether (DGEBA, molecular weight: 348), 10.11g of sebacic acid, 1.32g of zinc acetylacetonate and 14.42g of glass fiber, uniformly mixing, pouring into an internal mixer, dynamically vulcanizing at 180 ℃ under the condition of 80 r/min, and after 25 minutes, finishing the reaction to obtain the epoxy resin composite material with the glass fiber filling amount of 50 wt%.
Example 4:
under the condition of room temperature, respectively weighing 17.40g of bisphenol A diglycidyl ether (DGEBA, molecular weight: 348), 5.71g of glutaric anhydride, 1.32g of zinc acetylacetonate and 1.22g of glass fiber, uniformly mixing, pouring into an internal mixer, dynamically vulcanizing at 180 ℃ under the condition of 80 r/min, and finishing the reaction after 15 minutes to obtain the epoxy resin composite material with the glass fiber filling amount of 5 wt%.
Example 5:
under the condition of room temperature, respectively weighing 17.40g of bisphenol A diglycidyl ether (DGEBA, molecular weight: 348), 10.11g of sebacic acid, 1.32g of zinc acetylacetonate and 1.44g of glass fiber into a beaker, uniformly mixing, pouring into an internal mixer, dynamically vulcanizing at 200 ℃ at 50 r/min, and after 10 minutes, finishing the reaction to obtain the epoxy resin composite material with the glass fiber filling amount of 5 wt%.
Example 6:
under the condition of room temperature, respectively weighing 17.40g of bisphenol A diglycidyl ether (DGEBA, molecular weight: 348), 10.11g of sebacic acid, 1.32g of zinc acetylacetonate and 0.288g of glass fiber into a beaker, uniformly mixing, pouring into an internal mixer, dynamically vulcanizing at 160 ℃ and 50 r/min, and after 40 minutes, finishing the reaction to obtain the epoxy resin composite material with the glass fiber filling amount of 1 wt%.
Example 7:
under the condition of room temperature, respectively weighing 17.40g of bisphenol A diglycidyl ether (DGEBA, molecular weight: 348), 10.11g of sebacic acid, 2.64g of zinc acetylacetonate and 1.44g of glass fiber, uniformly mixing, pouring into an internal mixer, dynamically vulcanizing at 180 ℃ under the condition of 80 revolutions per minute, and after 20 minutes, finishing the reaction to obtain the epoxy resin composite material with the glass fiber filling amount of 5 wt%.
Comparative example 1:
respectively weighing 17.40g of DGEBA, 10.11g of sebacic acid and 1.32g of zinc acetylacetonate into a beaker at room temperature, uniformly mixing, transferring into an internal mixer, carrying out dynamic crosslinking at 180 ℃ at 80 rpm, and finishing the reaction after 20 minutes to obtain the pure epoxy resin material.
Comparative example 2:
respectively weighing 17.40g of DGEBA, 10.11g of sebacic acid, 1.32g of zinc acetylacetonate and 1.44g of glass fiber into a beaker at room temperature, uniformly mixing, transferring into an internal mixer, mixing for 5 minutes at 80 revolutions per minute at room temperature to obtain a uniform mixture, and then putting the uniform mixture into an oven at 180 ℃ for static curing for 60 minutes to obtain the epoxy resin composite material with the glass fiber content of 5 wt%.
Static curing is to mix all reactants uniformly and then carry out curing reaction in a static state to obtain a cross-linked polymer, and usually, the cross-linked polymer is formed in one step to obtain a product with a required shape. The dynamic crosslinking is that the solidification reaction of reactants is carried out under the strong shearing action of a rotor, when the crosslinked polymer is formed by the reaction, because the exchange reaction of dynamic covalent bonds exists between the network polymers formed by crosslinking, although the network structure still exists, the network topological structure can be rearranged, the melt flowability is the same as that of the thermoplastic linear polymer, when the crosslinking degree is higher and higher, the network rearrangement becomes very slow, the static solidified melt becomes a solid substance, and the dynamic crosslinking is finished.
The material test performance of the examples and comparative examples of the present invention is as follows:
table 1 performance results for composites prepared in the examples
Scanning electron micrographs of example 1 and comparative example 2 referring to fig. 1, it is clear that the glass fibers are well dispersed in the composite matrix of example 1 and the agglomeration is evident in comparative example 2, which indicates that the technique of the invention facilitates the dispersion of the chopped glass fibers, whereas the static curing technique employed at the present stage inevitably leads to the agglomeration of the chopped glass fibers.
As can be seen from the above examples, the present invention provides for the dynamic crosslinking or dynamic vulcanization of chopped glass fibers, along with epoxy monomers, curing agents, and transesterification catalysts, in polymer processing equipment (internal mixers, twin screw extruders) under high shear. The method of the invention utilizes the strong shearing action to realize the good dispersion of the glass fiber in the crosslinking epoxy resin under the condition of not carrying out surface modification on the glass fiber, and the well-dispersed glass fiber can be locked in the matrix along with the crosslinking of the polymer matrix along with the progress of dynamic vulcanization, thereby avoiding the secondary agglomeration of the glass fiber, realizing the good and stable dispersion of the glass fiber in the epoxy resin matrix and ensuring the mechanical property of the material. Therefore, the invention realizes the high-efficiency, low-cost and rapid preparation of the epoxy resin/chopped glass fiber composite material, and has important significance for scale production and industrial application thereof.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the glass fiber reinforced epoxy resin composite material is characterized by comprising the following steps:
mixing an epoxy resin monomer, an acid curing agent, an ester exchange catalyst and chopped glass fibers to obtain a mixture; and pouring the mixture into polymer processing equipment, and carrying out dynamic vulcanization under the action of strong shearing to obtain the glass fiber reinforced epoxy resin composite material.
2. The method according to claim 1, wherein the epoxy resin monomer is an organic compound having two or more epoxy groups in a molecule.
3. The method of claim 2, wherein the epoxy monomer is bisphenol a diglycidyl ether.
4. The preparation method according to claim 1, wherein the acid curing agent is one or more of polybasic acid anhydride and polybasic acid; wherein the molar ratio of the carboxyl to the epoxy resin monomer is 1: 1.
5. The process according to any one of claims 1 to 4, wherein the dynamic vulcanization is carried out at a rotation speed of 50 to 80 rpm and a temperature of 160 ℃ to 200 ℃.
6. The method of claim 5, wherein the transesterification catalyst has a decomposition temperature greater than 160 ℃.
7. The method according to claim 6, wherein the transesterification catalyst is zinc acetylacetonate.
8. The method according to claim 6, wherein the transesterification catalyst is added in a molar amount of 5 to 20% based on the molar amount of epoxy groups in the epoxy resin monomer.
9. The method for preparing the glass fiber reinforced plastic composite material according to claim 5, wherein the chopped glass fiber has a diameter of 0.04-19 μm and a length of 2-5000 μm; the mass percentage of the chopped glass fiber is between 0 and 50 percent.
10. The method of claim 5, wherein the polymer processing equipment is one of an internal mixer, a single screw extruder, and a twin screw extruder.
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