CN115057989A - Grafted polyether toughened epoxy resin composite material and preparation method and application thereof - Google Patents
Grafted polyether toughened epoxy resin composite material and preparation method and application thereof Download PDFInfo
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- CN115057989A CN115057989A CN202210797821.7A CN202210797821A CN115057989A CN 115057989 A CN115057989 A CN 115057989A CN 202210797821 A CN202210797821 A CN 202210797821A CN 115057989 A CN115057989 A CN 115057989A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 88
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 88
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 60
- 229920000570 polyether Polymers 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000004593 Epoxy Substances 0.000 claims abstract description 48
- 239000012948 isocyanate Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000009257 reactivity Effects 0.000 claims abstract description 7
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 4
- 229920005862 polyol Polymers 0.000 claims abstract 3
- 150000003077 polyols Chemical class 0.000 claims abstract 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 239000000945 filler Substances 0.000 claims 2
- 238000007142 ring opening reaction Methods 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 11
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 33
- 238000012360 testing method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OEIWCIOTLNSUKO-UHFFFAOYSA-N N=C=O.C1=CNC=N1 Chemical compound N=C=O.C1=CNC=N1 OEIWCIOTLNSUKO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/584—Epoxy resins having nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Spectroscopy & Molecular Physics (AREA)
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Abstract
The invention relates to a grafted polyether toughened epoxy resin composite material and a preparation method and application thereof, wherein an epoxy resin system and an imidazole curing agent are mixed according to a certain proportion, and the epoxy resin system and the imidazole curing agent are reacted to open a loop and extend a chain so as to improve the molecular weight and reduce the reactivity of N on an imidazole ring, thereby preparing an epoxy resin-imidazole pre-product; by adjusting the reaction sequence, two isocyanate groups of isocyanate are respectively reacted with hydroxyl groups in the epoxy resin-imidazole pre-product and polyether polyol for grafting (or crosslinking), so that the epoxy resin composite material can be prepared, the problems that the storage performance of the material is influenced due to mutual reaction when an imidazole curing agent and an isocyanate curing agent mutually promote the curing of the epoxy resin in the conventional epoxy resin curing are solved, and meanwhile, the mechanical property of the material is improved on the premise of not influencing other properties, and the toughness and the impact resistance are improved. The method has simple process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of nano materials, and relates to a grafted polyether toughened epoxy resin composite material, and a preparation method and application thereof.
Background
The industrial production of the epoxy resin field in China has been greatly developed since 1958, the application field is continuously expanded, and the epoxy resin has been widely applied to the fields of coatings, electrical insulating materials, fiber resin materials, adhesives and the like. The application of the epoxy resin depends on a compounding technology, and the design of a formula is important except equipment and a process. The selection and combination of the epoxy resin, curing agent and its associated additives is required to achieve the desired target properties. The epoxy resin is a high polymer containing two or more epoxy groups in the molecule, and can be subjected to cross-linking reaction with a curing agent to form a high polymer with a three-dimensional network structure. Bisphenol A epoxy resin is a high molecular compound generated by reacting bisphenol A and epichlorohydrin in the presence of sodium hydroxide, and is a variety with the largest yield and the widest use in epoxy resin. The cured product has the advantages of high strength, high bonding strength, high corrosion resistance, high electrical property, certain toughness, heat resistance and the like, and is widely applied.
Imidazole-based curing agents are compounds having an imidazole structure in their molecular structure, and have been widely used as anionic polymerization-type curing agents because they contain a secondary amine group and a tertiary amine group and are reactive with an epoxy group in an epoxy resin. The isocyanate is also used as a curing agent of the epoxy resin, and can react with the imidazole curing agent when being mutually promoted with the imidazole curing agent to cure the epoxy resin, so that the storage performance of the material is influenced, and the requirement of long-term storage of a single-component epoxy resin system in the application of the final material cannot be met. Furthermore, the high reactivity of the curing agent used and the high crosslink density and the specific molecular structure of the epoxy resin can affect the storage, toughness and impact resistance of the resin material. Therefore, a method is urgently needed to solve the problem that two curing agents can react with each other when coexisting, improve the mechanical property of the material and improve the toughness and the impact resistance on the premise of not influencing other properties.
Disclosure of Invention
In view of the above, an object of the present invention is to provide two methods for preparing a grafted polyether toughened epoxy resin composite material; the second purpose is to provide a grafted polyether toughened epoxy resin composite material; the third purpose is to provide the application of the grafted polyether toughened epoxy resin composite material in the conductive silver paste material, solve the problem that the storage performance of the material is influenced by mutual reaction of imidazole curing agents and isocyanate curing agents which mutually promote the curing of the epoxy resin in the existing epoxy resin curing, and simultaneously improve the mechanical property of the resin material.
In order to achieve the purpose, the invention provides the following technical scheme:
two preparation methods of the grafted polyether toughened epoxy resin composite material comprise the following steps:
the method comprises the following steps: (1) mixing an epoxy resin system with an imidazole curing agent, carrying out pre-reaction chain extension to improve the molecular weight and increase the number of active hydroxyl groups to obtain an epoxy resin-imidazole pre-product; (2) adding polyether into isocyanate to carry out pre-reaction, and reacting isocyanate groups with higher activity with terminal hydroxyl groups of the polyether to prepare an isocyanate-polyether pre-product; (3) adding isocyanate-polyether pre-product into epoxy resin-imidazole pre-product for reaction grafting to prepare the toughened epoxy resin-imidazole-isocyanate-polyester material with good mechanical property.
Preferably, in the step (1), the epoxy resin system is that the mass ratio of epoxy resin to dipropylene glycol methyl ether solvent is 1: 1-2: 1, mixing.
Preferably, the imidazole is added in the step (1) in an amount of 4-6 wt% of the epoxy resin.
Preferably, the pre-reaction condition of the epoxy resin system and the imidazole curing agent in the step (1) is that the epoxy resin system and the imidazole curing agent react for 20-30 min at 90 ℃.
Preferably, the isocyanate in step (2) is an asymmetric isocyanate with a different reactivity, i.e. one of Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI).
Preferably, the polyether used in step (2) is a polyether having active hydroxyl groups at both ends, and may be replaced by a polyester having active hydroxyl groups, and hydroxyl-terminated materials with different properties may be introduced according to different properties of the resin material, so as to be suitable for different scenes.
Preferably, the reaction condition of the isocyanate and the polyether in the step (2) is that the reaction is carried out for 1-2 hours at 40-50 ℃ under the air-removing condition, so that the hydroxyl-terminated polyether prepolymer can realize complete end capping of isocyanate groups.
Preferably, n is used in step (2) -NCO :n -OH Hydroxyl polyether is added into isocyanate according to the proportion of 2.0-2.1: 1.0.
Preferably, the isocyanate-polyether pre-product added to the epoxy resin-imidazole pre-product in step (3) is 50-70 wt% of the epoxy resin (the molar ratio of-OH in the epoxy resin-imidazole pre-product to-NCO in the isocyanate-polyether pre-product is 1: 1).
Preferably, the reaction condition of the epoxy resin-imidazole pre-product and the isocyanate-polyether pre-product in the step (3) is 90-100 ℃ for 2 hours.
The first method is that epoxy resin-imidazole pre-product and diisocyanate end-capped polyether two-component resin system such as TDI or IPDI, etc. are mixed, grafted or cross-linked for subsequent curing.
The second method comprises the following steps: (1) mixing an epoxy resin system with an imidazole curing agent, carrying out pre-reaction chain extension to improve the molecular weight and increase the number of active hydroxyl groups to obtain an epoxy resin-imidazole pre-product; (2) adding isocyanate into the epoxy resin-imidazole pre-product obtained in the step (1), uniformly stirring and reacting to obtain an epoxy resin-imidazole-isocyanate resin material, so as to obtain an epoxy resin-imidazole-isocyanate material; (3) hydroxyl polyether is added into the epoxy resin-imidazole-isocyanate material for reaction and solidification, and the epoxy resin-imidazole-isocyanate material with good mechanical property is prepared.
Preferably, in the step (1), the epoxy resin system is that the mass ratio of epoxy resin to dipropylene glycol methyl ether solvent is 1: 1-2: 1, mixing.
Preferably, the imidazole is added in the step (1) in an amount of 4-6 wt% of the epoxy resin.
Preferably, the pre-reaction condition of the epoxy resin system and the imidazole curing agent in the step (1) is that the epoxy resin system and the imidazole curing agent react for 20-30 min at 90 ℃.
Preferably, the isocyanate in step (2) is an asymmetric isocyanate with a different reactivity, i.e. one of Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI).
Preferably, in the step (2), the amount of TDI or IPDI added to the epoxy resin-imidazole pre-product is 8-16 wt% of the epoxy resin, so that the isocyanate group with higher activity reacts with the hydroxyl group in the epoxy resin-imidazole pre-product to perform half-blocking, and the isocyanate group with lower activity is retained to perform subsequent reaction.
Preferably, the reaction condition of the isocyanate and the epoxy resin-imidazole pre-product in the step (2) is that the reaction is carried out for 20-30 min at 40-50 ℃.
Preferably, the polyether used in step (3) is a polyether having active hydroxyl groups at both ends, and may be replaced by a polyester having active hydroxyl groups, and the introduced hydroxyl groups have different properties, so that different properties of the resin material can be improved, and the resin material is suitable for different scenes.
Preferably, the isocyanate used in step (3): the hydroxyl-terminated polyether is added according to the molar ratio of 2.0-2.1: 1.0, so that the hydroxyl-terminated polyether prepolymer can realize complete end capping of isocyanate groups.
Preferably, the hydroxyl-terminated polyether and the epoxy resin-imidazole-isocyanate material in the step (3) are reacted for 2 hours at the temperature of 90-100 ℃.
And the second method is a diisocyanate-terminated imidazole-epoxy + polyether two-component resin system such as TDI or IPDI and the like, and subsequent curing is carried out by mixing, grafting or crosslinking.
The grafted polyether toughened epoxy resin composite material is prepared by the two preparation methods of the grafted polyether toughened epoxy resin composite material.
The application of the grafted polyether toughened epoxy resin composite material in a conductive silver paste material.
The invention has the beneficial effects that:
the invention discloses a grafted polyether toughened epoxy resin composite material, which takes epoxy resin as a main body, improves molecular weight by adding imidazole to react with the epoxy resin for chain extension and increases the number of active hydroxyl groups, can ensure that active groups (secondary amino and tertiary amino) of the imidazole completely react under the condition that the epoxy resin-imidazole system is completely reacted as far as possible before gelation, simultaneously keeps the fluidity of the system after adding new active hydroxyl groups, thus the reactive groups do not react with the imidazole when adding isocyanate, and then utilizes the reaction activity difference of two isocyanate groups in asymmetric isocyanate such as toluene-2, 4-diisocyanate (TDI) and the like to react with the terminal hydroxyl groups of polyether for grafting (or crosslinking) under the condition of low temperature so as to lead the isocyanate group with higher reaction activity of the isocyanate to be blocked and reduce the reaction activity at room temperature and keep lower active isocyanate groups for subsequent curing, therefore, the storage stability of a system and the low-temperature curing performance of a final material are ensured, meanwhile, a flexible chain segment is introduced into the material to realize toughening, active hydroxyl generated by pre-reaction chain extension of low-reactivity isocyanate groups and epoxy resin at 90 ℃ is reacted, bridged, crosslinked and cured, a polyether flexible chain segment is introduced into the resin material, and the toughness of the cured material is improved; the resin material has good fluidity when stored at room temperature for more than 14 days, the fluidity of two types of two-component resin products is good, the material with good mechanical property can be obtained only by subsequent composite particle or direct curing, and the mechanical property is enhanced compared with the material without introduced polyether after curing; the preparation method of the resin material is simple and easy to operate, is suitable for expanded production, and can provide a new strategy for forming processing and widening application scenes in different occasions when the resin material is used in the conductive silver paste material.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For a better understanding of the objects, aspects and advantages of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph showing the effect of viscosity on epoxy resin materials prepared in examples 1 and 4 of the present invention and comparative example 1;
FIG. 2 is a DSC chart of the epoxy resin material prepared in examples 1, 3 and 4 of the present invention;
FIG. 3 is a stress-strain graph of the epoxy resin materials prepared in example 1 of the present invention and comparative example 2;
FIG. 4 is a graph showing a comparison of the elongation at break of the epoxy resin materials prepared in examples 1 to 4 of the present invention and comparative example 2;
FIG. 5 is a graph showing a comparison of tensile strengths of epoxy resin materials prepared in examples 1 to 4 of the present invention and comparative example 2.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Wherein the showings are for the purpose of illustration only and not for the purpose of limiting the invention, shown in the drawings are schematic representations and not in the form of actual drawings; for a better explanation of the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if there is an orientation or positional relationship indicated by terms such as "upper", "lower", "left", "right", "front", "rear", etc., based on the orientation or positional relationship shown in the drawings, it is only for convenience of description and simplification of description, but it is not an indication or suggestion that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes, and are not to be construed as limiting the present invention, and the specific meaning of the terms may be understood by those skilled in the art according to specific situations.
Example 1
Preparation of grafted polyether toughened epoxy resin material
(1) Adding 4 wt% of 2-ethyl-4-methylimidazole (2E4MI) into the epoxy resin dissolved by 50 wt% of dipropylene glycol methyl ether solvent, and reacting at 90 ℃ for 30min to obtain an epoxy resin-imidazole pre-product;
(2) n at the temperature of 45 ℃ under the protection atmosphere of dry nitrogen -NCO :n -OH Adding polypropylene glycol-1000 (PPG-1000) dropwise into toluene-2, 4-diisocyanate (TDI) according to the proportion of 2:1, and reacting for 2 hours at the temperature to prepare an isocyanate-polyether pre-product;
(3) and (2) adding 50 wt% of the isocyanate-polyether pre-product prepared in the step (2) into the epoxy resin-imidazole pre-product in the step (1), mechanically stirring for 15min, uniformly mixing, ultrasonically treating for 1h, placing in a 50 ℃ oven, vacuumizing for many times, and removing bubbles to obtain a uniform toughened epoxy resin material, so as to perform latency test, curing behavior test and cured product mechanical property test.
Example 2
Preparation of grafted polyether toughened epoxy resin composite material
(1) Adding 5 wt% of 2E4MI into epoxy resin dissolved by 50 wt% of dipropylene glycol methyl ether solvent, and reacting at 90 ℃ for 30min to obtain an epoxy resin-imidazole pre-product;
(2) under the protection of dry nitrogen, at the temperature of 45 ℃ and n -NCO :n -OH Dripping PPG-1000 into TDI according to the proportion of 2:1, and reacting for 2h at the temperature to prepare an isocyanate-polyether pre-product;
(3) and (2) adding 60 wt% of the isocyanate-polyether pre-product prepared in the step (2) into the epoxy resin-imidazole pre-product in the step (1), mechanically stirring for 15min, uniformly mixing, ultrasonically treating for 1h, placing in a 50 ℃ oven, vacuumizing for many times, and removing bubbles to obtain a uniform toughened epoxy resin material, so as to perform latency test, curing behavior test and cured product mechanical property test.
Example 3
Preparation of grafted polyether toughened epoxy resin composite material
(1) Adding 6 wt% of 2E4MI into epoxy resin dissolved by 50 wt% of dipropylene glycol methyl ether solvent, and reacting at 90 ℃ for 30min to obtain an epoxy resin-imidazole pre-product;
(2) under the protection of dry nitrogen, at the temperature of 45 ℃ and n -NCO :n -OH Dripping PPG-1000 into TDI according to the proportion of 2:1, and reacting for 2h at the temperature to prepare an isocyanate-polyether pre-product;
(3) and (2) adding 60 wt% of the isocyanate-polyether pre-product prepared in the step (2) into the epoxy resin-imidazole pre-product in the step (1), mechanically stirring for 15min, uniformly mixing, ultrasonically treating for 1h, placing in a 50 ℃ oven, vacuumizing for many times, and removing bubbles to obtain a uniform toughened epoxy resin material, so as to perform latency test, curing behavior test and cured product mechanical property test.
Example 4
Preparation of grafted polyether toughened epoxy resin composite material
(1) Adding 4 wt% of 2E4MI into epoxy resin dissolved by 50 wt% of dipropylene glycol methyl ether solvent, and reacting at 90 ℃ for 30min to obtain an epoxy resin-imidazole pre-product;
(2) to epoxy-imidazole pre-productsAdding 16 wt% of TDI, stirring uniformly, introducing N at 45 DEG C 2 Reacting for 2h to prepare the epoxy resin-imidazole-isocyanate pre-product.
(3) Adding n to the epoxy resin-imidazole-isocyanate pre-product of step (2) -NCO :n -OH Adding PPG-1000 in a ratio of 2:1, mechanically stirring for 15min, uniformly mixing, performing ultrasonic treatment for 1h, placing in an oven at 50 ℃ for multiple times, vacuumizing and removing bubbles to obtain a uniform toughened epoxy resin material, and performing latency test, curing behavior test and cured product mechanical property test.
Comparative example 1
Preparation of epoxy-imidazole-isocyanate resin Material
(1) Adding 4 wt% of 2E4MI into the epoxy resin dissolved by 50 wt% of dipropylene glycol methyl ether solvent, and stirring for 15min to obtain an epoxy resin-imidazole pre-product;
(2) and (2) adding 16 wt% of TDI into the epoxy resin-imidazole pre-product obtained in the step (1), mechanically stirring for 15min, and uniformly mixing to obtain the epoxy resin material cured by imidazole-isocyanate.
The epoxy resin-imidazole pre-product of comparative example 1 cured rapidly after the addition of TDI, losing processability, indicating that the storage stability of the epoxy resin-imidazole system without pre-treatment is not ideal.
Comparative example 2
Preparation of epoxy-imidazole-isocyanate resin Material
(1) Adding 4 wt% of 2E4MI into epoxy resin dissolved in 50 wt% of dipropylene glycol methyl ether solvent, and reacting at 90 ℃ for 30min to obtain epoxy resin-imidazole pre-product
(2) Adding 16 wt% of TDI into the epoxy resin-imidazole pre-product obtained in the step (1), mechanically stirring for 15min, uniformly mixing, ultrasonically treating for 1h, placing in a 50 ℃ oven, vacuumizing for many times, and removing bubbles to obtain a uniform toughened epoxy resin material, so as to carry out latency test, curing behavior test and cured product mechanical property test.
Comparative example 3
Preparation of grafted polyether toughened epoxy resin composite material
(1) Adding 4 wt% of 2E4MI into epoxy resin dissolved by 50 wt% of dipropylene glycol methyl ether solvent, and reacting at 90 ℃ for 30min to obtain an epoxy resin-imidazole pre-product;
(2) adding 16 wt% of TDI into the epoxy resin-imidazole pre-product, stirring uniformly, and introducing N at 45 DEG C 2 Reacting for 2h to prepare the epoxy resin-imidazole-isocyanate pre-product.
(3) Adding n to the epoxy resin-imidazole-isocyanate pre-product of step (2) -NCO :n -OH Adding PPG-1000 in the proportion of 1.9:1, mechanically stirring for 15min, uniformly mixing, ultrasonically treating for 1h, placing in a 50 ℃ oven, vacuumizing for many times, and removing bubbles to obtain the uniform toughened epoxy resin material, and carrying out latency test, curing behavior test and cured product mechanical property test.
Storage stability test
The toughened epoxy resin materials prepared in the steps (2) of the examples 1 and 4 and the comparative example 1 are placed at 25 ℃ to observe the change of the viscosity of the system, the storage stability of the toughened epoxy resin materials is examined, the test result is shown in a figure 1, and compared with the comparative example 1, the storage stability of the examples 1 and 4 is greatly improved, and is increased from 1 day to 14 days.
Curing behavior test results
The toughened epoxy resin material prepared in the step (3) of the embodiments 1, 3 and 4 is tested for initial temperature, peak temperature and end temperature by a DSC thermal analysis tester, the testing temperature range is 25-200 ℃, the heating rate is 5 ℃/min, and a DSC curve obtained by testing in a nitrogen atmosphere is shown in figure 2. It can be seen that the epoxy resin material starts to cure at 90-100 c, the initial temperature increasing with increasing imidazole addition. The epoxy resin material has good storage stability and high activity at room temperature, and the curing temperature can be regulated and controlled between 90 ℃ and 100 ℃.
Mechanical property test of cured product
The mechanical property test method of the condensate comprises the following steps: pouring the toughened epoxy resin material obtained in the embodiment into a polytetrafluoroethylene mold, and curing for 2h at 90 ℃. Mechanical properties of the cured product were measured at room temperature using a universal tester, each sample was tested in parallel 5 times, and the average results were taken for epoxy resinsThe tensile strength, the elastic modulus and the elongation at break are all obviously improved, and the results are shown in figures 3-5. It can be seen that the elongation at break of examples 1 to 4 was increased by up to 3%, the tensile strength was increased from 24.17MPa to 31.52MPa, and the elongation at break and tensile strength of comparative example 3 were significantly lower than those of examples 1 to 4, compared to comparative example 2, indicating that this method achieves toughening effect, comparative example 3 being n -NCO :n -OH When hydroxyl-terminated polyether was added to isocyanate in a ratio of 1.9:1.0, the prepolymer did not achieve complete capping of the isocyanate groups, and it was seen that the elongation at break and tensile strength of the epoxy resin material were significantly inferior to those of examples 1-4.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the toughened epoxy resin composite material is characterized by comprising the following steps:
(1) mixing an epoxy resin system with an imidazole curing agent, carrying out pre-reaction, ring opening and chain extension to improve the molecular weight and reduce the reactivity of N on an imidazole ring at the same time, thus obtaining an epoxy resin-imidazole pre-product; (2) adding polyether polyol into isocyanate, and reacting isocyanate groups with higher activity with hydroxyl of polyether to prepare an isocyanate-polyether pre-product; (3) adding epoxy-imidazole pre-product to epoxy-imidazole pre-product: adding the isocyanate-polyether pre-product in a mass ratio of 1: 0.5-1: 08 to react and bridge to obtain the epoxy resin composite material.
2. The preparation method of the toughened epoxy resin composite material is characterized by comprising the following steps:
(1) mixing an epoxy resin system with an imidazole curing agent, carrying out pre-reaction, ring opening and chain extension to improve the molecular weight and reduce the reactivity of N on an imidazole ring at the same time, thus obtaining an epoxy resin-imidazole pre-product; (2) adding 8-16 wt% of isocyanate into the epoxy resin-imidazole pre-product obtained in the step (1), and reacting isocyanate groups with higher activity with hydroxyl in the epoxy resin-imidazole pre-product to obtain an epoxy resin-imidazole-isocyanate material; (3) and adding polyether glycol into the epoxy resin-imidazole-isocyanate material, and then reacting and curing to obtain the epoxy resin composite material.
3. The method according to claim 1 or 2, wherein the pre-reaction of the epoxy resin system and the imidazole curing agent in the step (1) is carried out at 80-90 ℃ for 25-30 min; in the step (1), the addition amount of the imidazole is 4-6 wt% of the epoxy resin.
4. The method according to claim 1 or 2, wherein the pre-reaction of isocyanate and hydroxyl in step (2) is carried out at 40-50 ℃ for 2-3 h under the condition of air removal.
5. The preparation method according to claims 1 and 2, wherein the reaction conditions for final curing of the system are 90-100 ℃ for 2 h.
6. The preparation method according to claim 1 and 2, wherein the isocyanate in step (2) is an asymmetric isocyanate with a reactivity difference, namely one of Toluene Diisocyanate (TDI) or isophorone diisocyanate (IPDI), wherein the TDI activity difference is above 40/80 ℃; the IPDI activity difference is above 50/90 ℃.
7. A preparation method as claimed in claim 1 and 2, characterized in that the polyether polyol used is polyether with active hydroxyl groups at both ends, or polyester with active hydroxyl groups, and hydroxyl-terminated materials with different properties are introduced according to different properties of the resin material so as to be suitable for different scenes.
8. The preparation method of claim 1 or 2, wherein the hydroxyl-terminated polyether is added in a molar ratio of isocyanate to polyether of 2.0:1 to 2.1:1, so as to ensure that the hydroxyl-terminated polyether prepolymer can be completely blocked by isocyanate groups.
9. The preparation method of claims 1 and 2, wherein the epoxy resin-imidazole-isocyanate-polyether resin material prepared in step (3) can be blended with a filler to prepare various resin materials before curing, so as to generate different effects and be applied to different scenes, wherein the filler is required not to react with an epoxy resin system.
10. The use of the grafted polyether toughened epoxy resin composite material of claims 1-9 in a conductive silver paste material.
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