CN114507335B - High-performance epoxy resin with adjustable thermal expansion coefficient and preparation method thereof - Google Patents
High-performance epoxy resin with adjustable thermal expansion coefficient and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 91
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 230000001276 controlling effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 68
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012346 acetyl chloride Substances 0.000 claims description 8
- 229940125904 compound 1 Drugs 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 229940126214 compound 3 Drugs 0.000 claims description 8
- 229940125898 compound 5 Drugs 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- CZYWAPBZHJZHJD-UHFFFAOYSA-N dibenzocyclooctadiene Chemical compound C1CCCC2=CC=CC=C2C2=CC=CC=C21 CZYWAPBZHJZHJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 6
- 230000008876 conformational transition Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000008602 contraction Effects 0.000 abstract 1
- 239000002952 polymeric resin Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 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 10
- 239000002131 composite material Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 230000006399 behavior Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 clays Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/52—Amino carboxylic acids
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of polymer materials, and particularly relates to a high-performance epoxy resin with an adjustable coefficient of thermal expansion (CTE= -10-50 ppm/K) and a preparation method thereof. The invention also relates to aromatic amine containing dibenzo eight-membered ring structure and a preparation method thereof, which are used for the epoxy resin curing agent and have the function of controlling the expansion coefficient of the epoxy resin. The epoxy resin is prepared by curing the aromatic amine curing agent with the structure and the epoxy resin precursor at a proper temperature, and the thermal expansion coefficient of the epoxy resin is regulated by changing the feeding ratio of the aromatic amine curing agent in the preparation process. The epoxy resin prepared by the invention has excellent heat resistance, thermal stability and mechanical property, and meanwhile, the polymer resin shows unique reversible thermal contraction behavior due to the conformational transition of the dibenzo eight-membered ring structure in the epoxy network. The high-performance epoxy resin with adjustable thermal expansion coefficient can be applied to the fields of precision devices and the like with strict requirements on dimensional stability.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a high-performance epoxy resin with an adjustable thermal expansion coefficient and a preparation method thereof.
Background
Epoxy resins are typical thermosetting polymeric materials with excellent adhesion and chemical resistance, good electrical insulation properties, high thermal stability and mechanical properties. These advantages have led to the wide application of epoxy resins in a variety of fields including coatings, packaging, and construction materials. However, epoxy resins have a relatively high coefficient of thermal expansion (60 to 80 ppm/K), limiting their use in some areas where high dimensional stability is required, such as the aerospace and microelectronics industries. In order to reduce the coefficient of thermal expansion of epoxy resins, researchers have typically incorporated inorganic particles or fibers into the epoxy matrix, including clays, carbon nanotubes, aluminum nitride, silica, ceramic materials, and the like. Inorganic compounds having negative thermal expansion (e.g. ZrW 2 O 8 、GaNMn 3 Etc.) are also often incorporated into epoxy resins to reduce the coefficient of thermal expansion.
Although fillers give epoxy resins higher thermal stability, these composites also have some problems. For inorganic compounds with negative thermal expansion, high loadings are typically required to achieve a satisfactory coefficient of thermal expansion for the epoxy resin, resulting in an increase in the density of the composite. In addition, for many inorganic compounds with negative thermal expansion, the effective temperature window is narrow and below room temperature, and is generally not suitable for practical application conditions. The orientation of the fibers in the composite may result in anisotropic thermal expansion with only a small or negative coefficient of thermal expansion in the axial direction. Fillers such as silica and clay have only a low coefficient of thermal expansion and are not negative, and therefore have great limitations in adjusting the coefficient of thermal expansion of epoxy composites. Meanwhile, for epoxy composite materials, the interface strength between the filler and the epoxy matrix is reduced due to the mismatch of the thermal expansion coefficients, and the compatibility and the dispersibility of the filler are also to be solved. Therefore, the invention of the intrinsic low expansion epoxy resin with adjustable thermal expansion coefficient has important significance, but has been recently reported.
The inventors et al reported, in combination with Jennifer Lu, university of california, usa, a crosslinked polyarylamide with significant negative expansion behavior (Shen Xingyuan, doctor's article, double denier university, 2016). Conformational changes of dibenzo-octatomic ring units in the polymer network have been shown to be associated with abnormal negative thermal expansion (nat. Chem.2013,5,1035). The dibenzo-octatomic ring mainly takes on a boat-like conformation at low temperature and is converted into a chair-like conformation at higher temperatures. In fact, the molecular structure has a great influence on its conformational transition. According to this mechanism, the inventors have obtained polyaramides (Macromolecules, 2018,51,8477) of positive, zero and negative thermal expansion in subsequent studies. Meanwhile, the inventors developed a synthetic route for a functional monomer having a dibenzo-octamembered ring unit, and prepared a linear polyarylamide (Macromolecules, 2018,51,1377) having a negative expansion behavior. Based on a large amount of synthesis, the dibenzo-octamembered ring-containing monomer with various functional groups is prepared and can be used for exploring more high-performance resins with negative thermal expansion behaviors.
The invention provides a method for synthesizing an aromatic amine curing agent containing a dibenzo eight-membered ring structure for the first time. The aromatic amine curing agent cures the epoxy resin to obtain the high-performance epoxy resin with adjustable thermal expansion coefficient. The prepared epoxy resin has excellent thermal performance and mechanical property, and the thermal expansion coefficient is adjustable within the range of-10.0-50 ppm/K. The curing agent containing dibenzo eight-membered ring is also suitable for various commercial epoxy resins, and has wide application prospect.
Disclosure of Invention
The invention aims to provide a high-performance epoxy resin with a controllable thermal expansion coefficient and a preparation method thereof.
The invention provides a high-performance epoxy resin with adjustable thermal expansion coefficient, which is epoxy resin containing dibenzo-octant ring structural units, takes an aromatic amine curing agent containing dibenzo-octant ring structure as a raw material, cures the epoxy resin, and adjusts the thermal expansion coefficient of the epoxy resin by changing the feeding ratio of the aromatic amine curing agent in the preparation process, and comprises the following specific steps:
dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove the solvent, heating and curing by a hot table, curing at 100-120 ℃ for 2-4 hours, and curing at 150-200 ℃ for 2-4 hours to obtain high-performance epoxy resin;
wherein the aromatic amine curing agent comprises two components, the first component is: aromatic amine (I) containing dibenzo eight-membered ring structure, and the structural formula is:
r1 and R2 are any one of H, methyl, ethyl, propyl, butyl and the like; r3 and R4 are Any one of methyl, ethyl, propyl, butyl, and the like;
the second component is a compound (II) with a general formula:
r isAny one of them;
in the curing reaction process, the proportion of the two components in the aromatic amine curing agent is regulated, so that the content of the dibenzo eight-membered ring structure in the epoxy resin is changed, and the thermal expansion coefficient of the obtained epoxy resin can be regulated.
In the invention, the second component compound (II) is controlled to account for 0-80% of the total aromatic amine curing agent, and the thermal expansion coefficient is adjustable between-10.0-50 ppm/K.
The invention provides a preparation method of high-performance epoxy resin with adjustable thermal expansion coefficient, which comprises the following specific steps: dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove the solvent, heating and curing by a hot table, curing at 100-120 ℃ for 2-4 hours, and curing at 150-200 ℃ for 2-4 hours to obtain the high-performance epoxy resin.
In the invention, the preparation method of the aromatic amine curing agent comprises the following synthetic route:
the method comprises the following specific steps:
(1) Under the anhydrous and anaerobic condition, adding solvent super-dry dichloromethane and 3-5 equivalents of aluminum chloride into the Schlenk tube; stirring for 5-10 minutes at the temperature of minus 30 to minus 25 ℃, adding 3-5 equivalents of acetyl chloride and 1 equivalent of dibenzocyclooctane, continuously stirring and reacting for 10-15 hours, and carrying out the reaction under the nitrogen atmosphere; after the reaction is finished, washing and purifying the reaction solution to obtain an intermediate compound 1;
(2) Adding 4-6 equivalents of solvent super-dry tetrahydrofuran and aluminum chloride into a reaction bottle under the nitrogen atmosphere, then adding 8-12 equivalents of sodium borohydride into the system, and stirring for 10-20 minutes; adding 1 equivalent of compound 1, and carrying out reflux reaction for 10-15 hours at 40-60 ℃; after the reaction is finished, the system is cooled to room temperature, and the intermediate compound 2 is obtained after washing and purification;
(3) Under the anhydrous and anaerobic condition, adding 40-60 mL of ultra-dry dichloromethane and 3-5 equivalents of aluminum chloride into a Schlenk tube; after cooling to-25 to-30 ℃, adding 3-5 equivalents of acetyl chloride into the mixture, and continuing stirring for 5-10 minutes; adding 1 equivalent of compound 2 into the solution, and continuously stirring and reacting for about 10-15 hours at the temperature of-25 to-30 ℃; after the reaction is completed, washing and purifying the reaction solution to obtain an intermediate compound 3;
(4) Adding 1 equivalent of compound 3 into a reaction bottle, wherein the solvent is methanol, and placing the reaction bottle into an oil bath pot at 55-60 ℃; then adding 10-20 equivalent sodium hypochlorite aqueous solution, and continuing stirring and reacting for 8-12 hours; after the reaction is finished, after the system is cooled to room temperature, obtaining an intermediate compound 4 after suction filtration and purification;
(5) Adding 1 equivalent of compound 4 and solvent methanol into a round-bottom flask, adding 8-12 equivalent of sodium hydroxide aqueous solution into the mixture after complete dissolution, and continuously stirring the reaction system for 10-15 hours at 55-60 ℃; after the reaction is finished, an intermediate compound 5 is obtained after acidification, suction filtration, washing and drying;
(6) 1 equivalent of compound 5 is dissolved in 80 to 120 equivalents of thionyl chloride, and reflux reaction is carried out for 10 to 15 hours at the temperature of 60 to 70 ℃; then removing thionyl chloride, adding solvent methylene dichloride and 8-12 equivalents of m-phenylenediamine, and stirring for reaction for 10-15 hours; then removing the solvent dichloromethane, washing and drying to obtain the compound 6.
The high-performance epoxy resin with the adjustable thermal expansion coefficient is applied to any field of electronic circuit boards, adhesives or packaging materials, or used for adjusting and controlling the thermal expansion behaviors of other materials.
The invention provides a preparation method of aromatic amine containing dibenzo-octatomic ring structure for the first time, the synthetic route is simple and feasible, and the product structure is correct through instrument analysis. The aromatic amine can be used as a curing agent for preparing epoxy resin, and the thermal expansion coefficient of the epoxy resin can be adjusted according to the content of the dibenzo-octamembered ring.
Drawings
FIG. 1 is a graph showing the change in the length of the epoxy resin obtained in examples 2 to 5 with temperature;
FIG. 2 is a graph showing the change in the length of the epoxy resin obtained in examples 6 to 9 with temperature;
FIG. 3 is a graph showing the length change rate of the epoxy resin obtained in example 5 during the temperature rising-constant temperature process;
FIG. 4 is a DSC test chart of the epoxy obtained in example 5;
fig. 5 is a FTIR test spectrum during the temperature increase of the epoxy resin obtained in example 5.
Detailed Description
The invention is further illustrated by the following examples.
Example 1 an aromatic amine curing agent containing a dibenzo-octamembered ring Structure(preparation of Compound 6)
Step one, 40mL of ultra-dry methylene chloride and anhydrous aluminum chloride (12.8 g,96.2 mmol) were added to a 100mL Shi Laike tube under anhydrous and anaerobic conditions. The Schlenk tube was placed in a cryostat and cooled to-30℃and acetyl chloride (7.55 g,96.2 mmol) was then added and stirred for 20 minutes. Dibenzocyclooctane (5.0 g,24.0 mmol) was added to the Schlenk tube and stirring was continued for 10-15 hours at-30 ℃. After the reaction, the reaction solution was washed and purified to obtain 16.7g of Compound 1 in a yield of 95%. 1 H NMR(400MHz,CDCl 3 )δ7.67–7.42(m,1H),7.04(d,J＝9.6Hz,1H),3.17(s,2H),2.48(s,2H). 13 C NMR(101MHz,CDCl 3 )δ197.94,197.92,145.70,145.56,140.14,140.05,135.41,135.34,130.12,129.97,129.69,129.42,34.66,34.53,34.36,26.50；
Step two, anhydrous tetrahydrofuran (60 mL) and aluminum chloride (7.5 g,56.3 mmol) were added to a round bottom flask and the reaction was carried out under nitrogen. Sodium borohydride (3.9 g,102.4 mmol) was added and stirred for 20 minutes, then compound 1 (3.0 g,10.3 mmol) was added to the system and reacted at 60℃for 10 to 15 hours. After the completion of the reaction, the reaction solution was washed and purified to obtain 2.2g of Compound 2 in a yield of 81%. 1 HNMR(400MHz,CDCl 3 )δ7.02(d,J＝7.9Hz,1H),6.94(s,2H),3.06(s,4H),2.61(q,J＝7.3Hz,2H),1.24(t,J＝8.6Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ141.88,141.20,141.11,129.74,129.71,129.37,125.42,125.38,35.74,35.65,35.31,35.25,28.36,15.63,15.61；
Step three, ultra-dry dichloromethane (30 mL) and anhydrous aluminum chloride (8.1 g,60.8 mmol) were added to a schlenk tube under nitrogen atmosphere. After cooling the system to-30 ℃, acetyl chloride (4.8 g,61.1 mmol) was added and stirring was continued for 10-15 minutes. Compound 2 (4.0 g,15.1 mmol) was added to the Schlenk tube and the system was allowed to react at-30℃for a further 10-15 hours. After the completion of the reaction, the reaction solution was washed and purified to obtain 2.5g of Compound 3, the yield was 47%. 1 H NMR(400MHz,CDCl 3 )δ7.33(s,1H),6.93(s,1H),3.10(d,J＝6.5Hz,4H),2.80(q,J＝7.5Hz,2H),2.54(s,3H),1.16(t,J＝7.5Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ201.62,144.39,142.58,137.58,135.55,132.09,131.05,34.86,34.72,29.75,26.73,15.90；
Step four, compound 3 (2 g,5.7 mmol) and methanol (50 mL) were added to a round bottom flask, then an aqueous sodium hypochlorite solution (50 mL) was added to the flask, and the reaction was continued with stirring at 60 ℃ for 10-15 hours. After completion of the reaction, 1.8g of compound 4 was obtained after filtration and purification in 84% yield. 1 H NMR(400MHz,CDCl 3 )δ7.56(s,1H),6.92(s,1H),3.86(s,3H),3.09(s,4H),2.88(q,J＝7.5Hz,2H),1.17(t,J＝7.5Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ167.98,144.83,144.23,137.72,132.22,131.78,51.65,34.83,34.45,27.13,15.86；
Step five, compound 4 (1 g,2.6 mmol) and methanol (25 mL) were added to a round bottom flask. After complete dissolution of compound 4, an aqueous solution of sodium hydroxide (1.1 g,26 mmol) was added thereto, and stirring was continued at 60℃for 10 to 15 hours. After the completion of the reaction, the reaction system was acidified, filtered, washed and dried to obtain compound 5 (0.9 g, 96%). 1 H NMR(400MHz,DMSO)δ12.58(s,1H),7.44(s,1H),6.92(s,1H),3.07(s,4H),2.78(dd,J＝14.7,7.3Hz,2H),1.05(t,J＝7.4Hz,3H). 13 C NMR(101MHz,DMSO)δ169.00,144.66,143.36,137.89,132.27,132.04,127.86,34.28,33.95,26.84,16.50；
Step six, compound 5 (0.5 g,1.4 mmol) was dissolved in SOCl in a 50mL round bottom flask 2 (10 mL) at 60℃backFlow-reacting for 10-15 hours, then removing SOCl 2 Adding the mixture into m-phenylenediamine and methylene dichloride, and stirring the mixture for 10 to 15 hours at room temperature. After the reaction was completed, methylene chloride was removed, and after washing, filtration and drying, 0.65g of compound 6 was obtained in 86% yield. 1 H NMR(400MHz,DMSO)δ9.93(s,1H),7.11(s,2H),7.01(s,1H),6.92(t,J＝8.0Hz,1H),6.76(d,J＝8.0Hz,1H),6.28(d,J＝7.9Hz,1H),5.10(s,2H),3.10(s,4H),2.64(q,J＝7.4Hz,2H),1.10(t,J＝7.5Hz,3H). 13 C NMR(101MHz,DMSO)δ168.20,149.35,142.28,140.40,139.57,137.94,135.34,131.04,129.23,109.96,108.25,105.93,34.89,34.54,25.87,16.27。
Example 2 preparation of Low expansion epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol), 4' -diaminodiphenyl ether (22.6 mg, 112.6. Mu. Mol) and triglycidyl isocyanurate (67.0 mg, 225.3. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours and at 150 to 200℃for 2 to 4 hours, to give a low-expansion epoxy resin.
Example 3 preparation of Low expansion epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol), 4' -diaminodiphenyl ether (11.3 mg, 56.3. Mu. Mol) and triglycidyl isocyanurate (44.6 mg, 150.2. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours and at 150 to 200℃for 2 to 4 hours, to give a low-expansion epoxy resin.
Example 4 preparation of negatively-expanded epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol), 4' -diaminodiphenyl ether (5.6 mg, 28.2. Mu. Mol) and triglycidyl isocyanurate (33.5 mg, 112.6. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours and at 150 to 200℃for 2 to 4 hours, to give a negative expansion epoxy resin.
Example 5 preparation of negatively-expanded epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol) and triglycidyl isocyanurate (22.3 mg, 75.1. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours, and at 150 to 200℃for 2 to 4 hours, to give a negative expansion epoxy resin.
Example 6 preparation of Low expansion epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol) and CYD-128 epoxy resin (42.1 mg, 225.3. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours, and at 150 to 200℃for 2 to 4 hours, to give a low-expansion epoxy resin.
Example 7 preparation of Low expansion epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol) and DER-331 epoxy resin (42.1 mg, 225.3. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours, and at 150 to 200℃for 2 to 4 hours, to give a low-expansion epoxy resin.
Example 8 preparation of Low expansion epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol) and R140 epoxy resin (42.1 mg, 225.3. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours, and at 150 to 200℃for 2 to 4 hours, to give a low-expansion epoxy resin.
Example 9 preparation of Low expansion epoxy resin
Compound 6 (30.0 mg, 56.3. Mu. Mol) and EPON 828 epoxy resin (42.1 mg, 225.3. Mu. Mol) were dissolved in N-methyl-2-pyrrolidone (1 mL), the solvent was removed by evaporation, and the mixture was cured by heating at a hot stage, and the curing reaction was allowed to stand at 100 to 120℃for 2 to 4 hours, and at 150 to 200℃for 2 to 4 hours, to give a low-expansion epoxy resin.
The epoxy resins obtained in examples 2 to 5 were subjected to thermal expansion property test, and the results are shown in fig. 1. Examples 2 to 5 have a thermal expansion coefficient of between-10 and 31.9ppm/K at a temperature range of-10 to 100℃depending on the content of dibenzo-octatomic rings in the epoxy resin.
Wherein the thermal expansion coefficient of the epoxy resin obtained in example 3 is 15.1ppm/K, and the epoxy resin is matched with the thermal expansion coefficient of metals such as copper (16-18 ppm/K), and when the epoxy resin is used as a composite material, material failure caused by mismatch of the thermal expansion coefficients can be avoided.
The negative expansion epoxy resin obtained in the example 4 has a thermal expansion coefficient of-10.0 ppm/K, can be compounded with other materials with larger thermal expansion coefficients, and can be used for regulating and controlling the overall thermal expansion coefficient of the composite material to meet the actual application demands.
The epoxy resin obtained in example 5 has a thermal expansion coefficient of-4.1 ppm/K, is close to zero expansion, and can be directly applied to the fields of precision devices and the like as a material with high dimensional stability.
The epoxy resin matrix used in examples 6-9 is a common commercial epoxy resin, and as shown in fig. 2, the thermal expansion coefficient measured is between 8.7 and 16.8ppm/K, and is close to that of ceramics and metals, and the epoxy resin matrix used as a composite material can reduce the risk of material failure.
The negative expansion behavior of the epoxy resin obtained in example 5 is due to the conversion of the dibenzo-octatomic ring from boat conformation to chair conformation. In testing the thermal expansion behavior, the temperature was raised from-10℃to 100℃and left at 100℃for 20 minutes, and the length change of the epoxy resin obtained in example 5 was observed. As shown in fig. 3, as the temperature increases, the sample length increases and then decreases, and as the temperature stays at 100 ℃, the length is still shrinking until equilibrium. This anomalous length profile results from a time-dependent conformational transition process.
The low or negative expansion behavior of the epoxy resins of examples 2-5 results from the conformational transition process of the dibenzo-octatomic ring, which should be accompanied by a change in energy. For examples 2 to 5, the DSC spectra (FIG. 4) of the resulting epoxy resins have a characteristic endothermic peak starting at 60℃which can be attributed to conformational transition.
In addition, the temperature-changing infrared test of the epoxy resin obtained in example 5 also shows that the temperature-increasing process occurs in the benzooctantConformational transition of the ring structural unit. According to theoretical calculations, intramolecular hydrogen bonds are present in the boat conformation, whereas the chair conformation is absent. As shown in FIG. 5, with increasing temperature, -NH-peak (3367 cm -1 ) The gradual weakening and narrowing, the remaining peaks are almost unchanged, indicating that the number of hydrogen bonds is decreasing, i.e. the boat conformation is decreasing, and changing into the chair conformation.
Claims (4)
1. The high-performance epoxy resin with the adjustable thermal expansion coefficient is characterized in that the high-performance epoxy resin is epoxy resin containing dibenzo-octant ring structural units, an aromatic amine curing agent containing dibenzo-octant ring structures is used as a raw material, the epoxy resin is cured, and the thermal expansion coefficient of the epoxy resin is adjusted by changing the feeding ratio of the aromatic amine curing agent in the preparation process, and the method comprises the following specific steps:
dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove the solvent, heating and curing by a hot table, curing at 100-120 ℃ for 2-4 hours, and curing at 150-200 ℃ for 2-4 hours to obtain high-performance epoxy resin;
wherein the aromatic amine curing agent comprises two components, the first component is: aromatic amine (I) containing dibenzo eight-membered ring structure, and the structural formula is:
r1 and R2 are any one of H, methyl, ethyl, propyl or butyl; r3 and R4 are Any one of methyl, ethyl, propyl or butyl;
the second component is a compound (II) with a general formula:
r isAny one of them;
in the curing reaction process, the proportion of two components in the aromatic amine curing agent is regulated, so that the content of the dibenzo eight-membered ring structure in the epoxy resin is changed, and the thermal expansion coefficient of the obtained epoxy resin can be regulated;
wherein: the preparation method of the aromatic amine curing agent comprises the following synthetic routes:
the method comprises the following specific steps:
(1) Under the anhydrous and anaerobic condition, adding solvent super-dry dichloromethane and 3-5 equivalents of aluminum chloride into the Schlenk tube; stirring for 5-10 minutes at the temperature of minus 30 to minus 25 ℃, adding 3-5 equivalents of acetyl chloride and 1 equivalent of dibenzocyclooctane, continuously stirring and reacting for 10-15 hours, and carrying out the reaction under the nitrogen atmosphere; after the reaction is finished, washing and purifying the reaction solution to obtain an intermediate compound 1;
(2) Adding 4-6 equivalents of solvent super-dry tetrahydrofuran and aluminum chloride into a reaction bottle under the nitrogen atmosphere, then adding 8-12 equivalents of sodium borohydride into the system, and stirring for 10-20 minutes; adding 1 equivalent of compound 1, and carrying out reflux reaction for 10-15 hours at 40-60 ℃; after the reaction is finished, the system is cooled to room temperature, and the intermediate compound 2 is obtained after washing and purification;
(3) Under the anhydrous and anaerobic condition, adding 40-60 mL of ultra-dry dichloromethane and 3-5 equivalents of aluminum chloride into a Schlenk tube; after cooling to-25 to-30 ℃, adding 3-5 equivalents of acetyl chloride into the mixture, and continuing stirring for 5-10 minutes; adding 1 equivalent of compound 2 into the solution, and continuously stirring and reacting for about 10-15 hours at the temperature of-25 to-30 ℃; after the reaction is completed, washing and purifying the reaction solution to obtain an intermediate compound 3;
(4) Adding 1 equivalent of compound 3 into a reaction bottle, wherein the solvent is methanol, and placing the reaction bottle into an oil bath pot at 55-60 ℃; then adding 10-20 equivalent sodium hypochlorite aqueous solution, and continuing stirring and reacting for 8-12 hours; after the reaction is finished, after the system is cooled to room temperature, obtaining an intermediate compound 4 after suction filtration and purification;
(5) Adding 1 equivalent of compound 4 and solvent methanol into a round-bottom flask, adding 8-12 equivalent of sodium hydroxide aqueous solution into the mixture after complete dissolution, and continuously stirring the reaction system for 10-15 hours at 55-60 ℃; after the reaction is finished, an intermediate compound 5 is obtained after acidification, suction filtration, washing and drying;
(6) 1 equivalent of compound 5 is dissolved in 80 to 120 equivalents of thionyl chloride, and reflux reaction is carried out for 10 to 15 hours at the temperature of 60 to 70 ℃; then removing thionyl chloride, adding solvent methylene dichloride and 8-12 equivalents of m-phenylenediamine, and stirring for reaction for 10-15 hours; then removing the solvent dichloromethane, washing and drying to obtain the compound 6.
2. The high performance epoxy resin with controllable thermal expansion coefficient according to claim 1, wherein the second component compound (II) is controlled to be 0-80% of the total aromatic amine curing agent, and the thermal expansion coefficient is adjustable between-10.0-50 ppm/K.
3. A method for preparing the high-performance epoxy resin with the adjustable thermal expansion coefficient according to claim 1, which is characterized by comprising the following specific steps: dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove the solvent, heating and curing by a hot table, curing at 100-120 ℃ for 2-4 hours, and curing at 150-200 ℃ for 2-4 hours to obtain high-performance epoxy resin; the preparation method of the aromatic amine curing agent comprises the following synthetic route:
the method comprises the following specific steps:
(1) Under the anhydrous and anaerobic condition, adding solvent super-dry dichloromethane and 3-5 equivalents of aluminum chloride into the Schlenk tube; stirring for 5-10 minutes at the temperature of minus 30 to minus 25 ℃, adding 3-5 equivalents of acetyl chloride and 1 equivalent of dibenzocyclooctane, continuously stirring and reacting for 10-15 hours, and carrying out the reaction under the nitrogen atmosphere; after the reaction is finished, washing and purifying the reaction solution to obtain an intermediate compound 1;
(2) Adding 4-6 equivalents of solvent super-dry tetrahydrofuran and aluminum chloride into a reaction bottle under the nitrogen atmosphere, then adding 8-12 equivalents of sodium borohydride into the system, and stirring for 10-20 minutes; adding 1 equivalent of compound 1, and carrying out reflux reaction for 10-15 hours at 40-60 ℃; after the reaction is finished, the system is cooled to room temperature, and the intermediate compound 2 is obtained after washing and purification;
(3) Under the anhydrous and anaerobic condition, adding 40-60 mL of ultra-dry dichloromethane and 3-5 equivalents of aluminum chloride into a Schlenk tube; after cooling to-25 to-30 ℃, adding 3-5 equivalents of acetyl chloride into the mixture, and continuing stirring for 5-10 minutes; adding 1 equivalent of compound 2 into the solution, and continuously stirring and reacting for about 10-15 hours at the temperature of-25 to-30 ℃; after the reaction is completed, washing and purifying the reaction solution to obtain an intermediate compound 3;
(4) Adding 1 equivalent of compound 3 into a reaction bottle, wherein the solvent is methanol, and placing the reaction bottle into an oil bath pot at 55-60 ℃; then adding 10-20 equivalent sodium hypochlorite aqueous solution, and continuing stirring and reacting for 8-12 hours; after the reaction is finished, after the system is cooled to room temperature, obtaining an intermediate compound 4 after suction filtration and purification;
(5) Adding 1 equivalent of compound 4 and solvent methanol into a round-bottom flask, adding 8-12 equivalent of sodium hydroxide aqueous solution into the mixture after complete dissolution, and continuously stirring the reaction system for 10-15 hours at 55-60 ℃; after the reaction is finished, an intermediate compound 5 is obtained after acidification, suction filtration, washing and drying;
(6) 1 equivalent of compound 5 is dissolved in 80 to 120 equivalents of thionyl chloride, and reflux reaction is carried out for 10 to 15 hours at the temperature of 60 to 70 ℃; then removing thionyl chloride, adding solvent methylene dichloride and 8-12 equivalents of m-phenylenediamine, and stirring for reaction for 10-15 hours; then removing the solvent dichloromethane, washing and drying to obtain the compound 6.
4. Use of a high performance epoxy resin with a controllable coefficient of thermal expansion according to claim 1, in any of the fields of electronic circuit boards, adhesives or packaging materials, or for controlling the thermal expansion behaviour of other materials.
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