CN114507335A - 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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- CN114507335A CN114507335A CN202210190845.6A CN202210190845A CN114507335A CN 114507335 A CN114507335 A CN 114507335A CN 202210190845 A CN202210190845 A CN 202210190845A CN 114507335 A CN114507335 A CN 114507335A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 95
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012346 acetyl chloride Substances 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 229940125898 compound 5 Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000000746 purification Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- CZYWAPBZHJZHJD-UHFFFAOYSA-N dibenzocyclooctadiene Chemical compound C1CCCC2=CC=CC=C2C2=CC=CC=C21 CZYWAPBZHJZHJD-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 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
- 230000009466 transformation Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 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 9
- 239000002131 composite material Substances 0.000 description 8
- 230000006399 behavior Effects 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000008876 conformational transition Effects 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
- 238000012360 testing method Methods 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008961 swelling Effects 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
- 230000002159 abnormal effect Effects 0.000 description 2
- -1 clays Substances 0.000 description 2
- 230000007423 decrease Effects 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
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 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
- 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
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 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
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction 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
- 230000003313 weakening effect Effects 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
- 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 and controllable 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 is used for epoxy resin curing agent and has the function of controlling the expansion coefficient of 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 adjusted 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 the polymer resin shows unique reversible thermal shrinkage behavior due to the conformation transformation of the dibenzo eight-membered ring structure in an epoxy network. The high-performance epoxy resin with adjustable and controllable thermal expansion coefficient can be applied to the fields of precision devices with strict requirements on dimensional stability and the like.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a high-performance epoxy resin with adjustable and controllable 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 widespread use of epoxy resins in a variety of fields, including coatings, packaging, and building materials, among others. However, the epoxy resin has a high thermal expansion coefficient (60-80 ppm/K), which limits the high requirements of some epoxy resinsApplications in the field of dimensional stability, for example in the field of aerospace and in the microelectronics industry. In order to reduce the coefficient of thermal expansion of epoxy resins, researchers have generally incorporated inorganic particles or fibers, including clays, carbon nanotubes, aluminum nitride, silica, ceramic materials, and the like, into the epoxy resin matrix. Inorganic compounds having negative thermal expansion (e.g. ZrW)2O8、GaNMn3Etc.) are also often incorporated into epoxy resins to reduce the coefficient of thermal expansion.
Although fillers impart greater thermal stability to epoxy resins, these composites also have problems. For inorganic compounds with negative thermal expansion, high loadings are generally required to achieve a satisfactory coefficient of thermal expansion for the epoxy resin, resulting in an increased density of the composite. In addition, for many inorganic compounds with negative thermal expansion, the effective temperature window is narrow and lower than room temperature, which is generally not suitable for practical application conditions. The orientation of the fibers in the composite material 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 thermal expansion, and thus have a great limitation in adjusting the coefficient of thermal expansion of epoxy resin composites. Meanwhile, for epoxy composite materials, the reduction of the interface strength between the filler and the epoxy matrix caused by the mismatch of the thermal expansion coefficients is also a big problem, and the compatibility and the dispersibility of the filler are also to be solved. Therefore, the invention of the intrinsic low-expansion epoxy resin capable of adjusting the thermal expansion coefficient has important significance, but is rarely reported at present.
The inventors have reported, in association with Jennifer Lu, the university of california, usa, a crosslinked polyarylamide with a pronounced negative swelling behavior (shenxing source, doctrine, university of fudan, 2016). Conformational changes of the dibenzo eight-membered ring units in the polymer network were shown to be associated with abnormal negative thermal expansion (nat. chem.2013,5,1035). The dibenzo-octatomic ring assumes mainly boat conformation at low temperatures and converts to chair conformation at higher temperatures. In fact, the molecular structure also has a large influence on its conformational transition. According to this mechanism, the inventors have obtained in subsequent studies polyaramids (Macromolecules,2018,51,8477) of positive, zero and negative thermal expansion. Meanwhile, the inventors developed a synthetic route of functional monomers having a dibenzo eight-membered ring unit and prepared linear polyarylamides (Macromolecules,2018,51,1377) having negative swelling behavior. On the basis of mass synthesis, the monomer containing dibenzo eight-membered ring 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 and controllable thermal expansion coefficient. The prepared epoxy resin has excellent thermal property and mechanical property, and the thermal expansion coefficient is adjustable within the range of-10.0 to 50 ppm/K. The curing agent containing dibenzo-eight-membered ring is also suitable for various commercial epoxy resins, and has wide application prospects.
Disclosure of Invention
The invention aims to provide a high-performance epoxy resin with adjustable and controllable thermal expansion coefficient and a preparation method thereof.
The invention provides a high-performance epoxy resin with adjustable and controllable thermal expansion coefficient, which is an epoxy resin containing a dibenzo-eight-membered ring structural unit, an aromatic amine curing agent containing a dibenzo-eight-membered ring structure is used as a raw material to cure the epoxy resin, the thermal expansion coefficient of the epoxy resin is adjusted by changing the feed ratio of the aromatic amine curing agent in the preparation process, and the specific steps are as follows:
dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove a 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 a high-performance epoxy resin;
the aromatic amine curing agent comprises two components, wherein the first component is as follows: aromatic amine (I) containing dibenzo eight-membered ring structure, the structural formula is:
r1 and R2 are any of H, methyl, ethyl, propyl, butyl, or the like; r3 and R4 are
Any of methyl, ethyl, propyl, butyl, and the like;
the second component is a compound (II) having the general formula:
r is
Any one of the above;
in the curing reaction process, the proportion of the two components in the aromatic amine curing agent is adjusted, 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 adjusted.
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 and controllable thermal expansion coefficient, which comprises the following steps: dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove a 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.
The preparation method of the aromatic amine curing agent comprises the following synthetic route:
the method comprises the following specific steps:
(1) adding solvent ultra-dry dichloromethane and 3-5 equivalents of aluminum chloride into a Schlenk tube under anhydrous and anaerobic conditions; stirring for 5-10 minutes at the temperature of-30 to-25 ℃, adding 3-5 equivalents of acetyl chloride and 1 equivalent of dibenzocyclooctane, continuing stirring and reacting for 10-15 hours, and reacting in a nitrogen atmosphere; after the reaction is finished, washing and purifying the reaction solution to obtain an intermediate compound 1;
(2) adding solvent ultra-dry tetrahydrofuran and aluminum chloride into a reaction bottle in an equivalent of 4-6 under the atmosphere of nitrogen, adding 8-12 equivalents of sodium borohydride into the system, and stirring for 10-20 minutes; adding 1 equivalent of the compound 1, and carrying out reflux reaction for 10-15 hours at 40-60 ℃; after the reaction is finished, cooling the system to room temperature, washing and purifying to obtain an intermediate compound 2;
(3) adding 40-60 mL of ultra-dry dichloromethane and 3-5 equivalents of aluminum chloride into a Schlenk tube under anhydrous and anaerobic conditions; after cooling to-25-30 ℃, adding 3-5 equivalent of acetyl chloride into the mixture, and continuously stirring for 5-10 minutes; adding 1 equivalent of the compound 2 into the solution, and continuously stirring and reacting at-25 to-30 ℃ for about 10 to 15 hours; after the reaction is finished, washing and purifying the reaction solution to obtain an intermediate compound 3;
(4) adding 1 equivalent of the compound 3 into a reaction bottle, wherein a solvent is methanol, and placing the reaction bottle in an oil bath pan at the temperature of 55-60 ℃; then adding 10-20 equivalents of sodium hypochlorite aqueous solution, and continuously stirring and reacting for 8-12 hours; after the reaction is finished, cooling the system to room temperature, and performing suction filtration and purification to obtain an intermediate compound 4;
(5) adding 1 equivalent of compound 4 and a solvent methanol into a round-bottom flask, completely dissolving, adding 8-12 equivalents of sodium hydroxide aqueous solution, and continuously stirring the reaction system at 55-60 ℃ for 10-15 hours; after the reaction is finished, obtaining an intermediate compound 5 through acidification, suction filtration, washing and drying;
(6) dissolving 1 equivalent of the compound 5 in 80-120 equivalents of thionyl chloride, and carrying out reflux reaction at 60-70 ℃ for 10-15 hours; removing thionyl chloride, adding dichloromethane serving as a solvent 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 application of the high-performance epoxy resin with the adjustable thermal expansion coefficient is applied to any field of electronic circuit boards, adhesives or packaging materials and the like, or is used for adjusting and controlling the thermal expansion behavior of other materials.
The invention provides a preparation method of aromatic amine containing dibenzo eight-membered 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 to prepare epoxy resin, and the thermal expansion coefficient of the epoxy resin can be adjusted according to the content of dibenzo eight-membered ring.
Drawings
FIG. 1 is a graph showing the change rate of the length of the epoxy resin obtained in examples 2 to 5 with temperature;
FIG. 2 is a graph showing the change in length of the epoxy resins obtained in examples 6 to 9 with temperature;
FIG. 3 is a graph showing the rate of change of length of the epoxy resin obtained in example 5 during temperature rise-holding;
FIG. 4 is a DSC chart of the epoxy resin obtained in example 5;
FIG. 5 shows FTIR test spectra during temperature rise of 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 eight-membered ring structure
Preparation of (Compound 6)
Step one, add 40mL of ultra dry methylene chloride and anhydrous aluminum chloride (12.8g,96.2mmol) to a 100mL Schlenk tube under anhydrous and anaerobic conditions. The Stirling tube was placed in a cryostat to cool to-30 ℃ and acetyl chloride (7.55g,96.2mmol) was added and stirred for 20 minutes. Dibenzocyclooctane (5.0g,24.0mmol) is added to a Schlenk tube and stirring is continued for 10-15 hours at-30 ℃. After the reaction, the reaction solution isAfter washing and purification, 16.7g of Compound 1 was obtained in 95% yield.1H NMR(400MHz,CDCl3)δ7.67–7.42(m,1H),7.04(d,J＝9.6Hz,1H),3.17(s,2H),2.48(s,2H).13C NMR(101MHz,CDCl3)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 (60mL) and aluminum chloride (7.5g,56.3mmol) were added to a round bottom flask and the reaction was carried out under nitrogen. Sodium borohydride (3.9g,102.4mmol) was added thereto, followed by stirring for 20 minutes, followed by adding compound 1(3.0g,10.3mmol) to the system, and reacting at 60 ℃ for 10 to 15 hours. After the reaction was completed, the reaction solution was washed and purified to obtain 2.2g of compound 2 with a yield of 81%.1HNMR(400MHz,CDCl3)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).13C NMR(101MHz,CDCl3)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 (30mL) and anhydrous aluminum chloride (8.1g,60.8mmol) were added to a schlenk tube under nitrogen atmosphere. After cooling the system to-30 ℃, acetyl chloride (4.8g,61.1mmol) was added and stirring continued for 10-15 minutes. Adding the compound 2(4.0g,15.1mmol) into a Schlenk tube, and continuing to react the system for 10-15 hours at-30 ℃. After completion of the reaction, the reaction solution was washed and purified to obtain 2.5g of Compound 3, which was found to be 47% in yield.1H NMR(400MHz,CDCl3)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).13C NMR(101MHz,CDCl3)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(2g, 5.7mmol) and methanol (50mL) were added to a round-bottom flask, then aqueous sodium hypochlorite (50mL) was added to the flask, and the reaction was continued with stirring at 60 ℃ for 10-15 hours. After completion of the reaction, filtration and purification gave 1.8g of Compound 4 in 84% yield.1H NMR(400MHz,CDCl3)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).13C NMR(101MHz,CDCl3)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(1g,2.6mmol) and methanol (25mL) were added to a round bottom flask. After the compound 4 was completely dissolved, an aqueous solution of sodium hydroxide (1.1g,26mmol) was added thereto, and stirring was continued at 60 ℃ for 10-15 hours. After completion of the reaction, the reaction system was acidified, filtered, washed and dried to obtain compound 5(0.9g, 96%).1H 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).13C 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(0.5g,1.4mmol) was dissolved in SOCl in a 50mL round bottom flask2(10mL), refluxing the reaction at 60 ℃ for 10 to 15 hours, and then removing SOCl2Adding m-phenylenediamine and dichloromethane, and stirring at room temperature for 10-15 hours. After completion of the reaction, dichloromethane was removed, washed, filtered and dried to obtain 0.65g of Compound 6, which was 86% in yield.1H 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).13C 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
Dissolving a compound 6(30.0mg,56.3 mu mol), 4' -diaminodiphenyl ether (22.6mg,112.6 mu mol) and triglycidyl isocyanurate (67.0mg,225.3 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove the solvent, heating and curing through a hot bench, and allowing the curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the low-expansion epoxy resin.
Example 3 preparation of Low-expansion epoxy resin
Dissolving a compound 6(30.0mg,56.3 mu mol), 4' -diaminodiphenyl ether (11.3mg,56.3 mu mol) and triglycidyl isocyanurate (44.6mg,150.2 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove a solvent, heating and curing through a hot bench, and allowing a curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the low-expansion epoxy resin.
Example 4 preparation of negative-expansion epoxy resin
Dissolving a compound 6(30.0mg,56.3 mu mol), 4' -diaminodiphenyl ether (5.6mg,28.2 mu mol) and triglycidyl isocyanurate (33.5mg,112.6 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove a solvent, heating and curing through a hot bench, and allowing a curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the negative expansion epoxy resin.
Example 5 preparation of negative-expansion epoxy resin
Dissolving a compound 6(30.0mg,56.3 mu mol) and triglycidyl isocyanurate (22.3mg,75.1 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove the solvent, heating and curing by a hot bench, and allowing a curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the negative expansion epoxy resin.
Example 6 preparation of Low-expansion epoxy resin
Dissolving the compound 6(30.0mg,56.3 mu mol) and CYD-128 epoxy resin (42.1mg,225.3 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove the solvent, heating and curing by a hot bench, and allowing the curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the low-expansion epoxy resin.
Example 7 preparation of Low-expansion epoxy resin
Dissolving the compound 6(30.0mg,56.3 mu mol) and DER-331 epoxy resin (42.1mg,225.3 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove the solvent, heating and curing by a hot bench, and allowing the curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the low-expansion epoxy resin.
Example 8 preparation of Low-expansion epoxy resin
Dissolving the compound 6(30.0mg,56.3 mu mol) and the R140 epoxy resin (42.1mg,225.3 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove the solvent, heating and curing by a hot bench, and allowing the curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the low-expansion epoxy resin.
Example 9 preparation of Low-expansion epoxy resin
Dissolving the compound 6(30.0mg,56.3 mu mol) and EPON 828 epoxy resin (42.1mg,225.3 mu mol) in N-methyl-2-pyrrolidone (1mL), volatilizing to remove the solvent, heating and curing by a hot bench, and allowing the curing reaction to stay at 100-120 ℃ for 2-4 hours and stay at 150-200 ℃ for 2-4 hours to obtain the low-expansion epoxy resin.
The results of the thermal expansion property test on the epoxy resins obtained in examples 2 to 5 are shown in FIG. 1. The thermal expansion coefficient of the epoxy resin of examples 2 to 5 is-10 to 31.9ppm/K at a temperature of-10 to 100 ℃ depending on the content of dibenzo-eight-membered ring in the epoxy resin.
The thermal expansion coefficient of the epoxy resin obtained in example 3 is 15.1ppm/K, and is matched with that of metals such as copper (16-18 ppm/K), so that when the epoxy resin is used as a composite material, material failure caused by mismatch of the thermal expansion coefficients can be avoided.
The thermal expansion coefficient of the negative expansion epoxy resin obtained in the embodiment 4 is-10.0 ppm/K, and the negative expansion epoxy resin can be compounded with other materials with larger thermal expansion coefficients to adjust and control the overall thermal expansion coefficient of the composite material so as to meet the requirements of practical application.
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 measured thermal expansion coefficient is between 8.7 and 16.8ppm/K, which is close to that of ceramics and metals, and the use of the epoxy resin matrix as a composite material can reduce the risk of material failure.
The negative swelling behavior of the epoxy resin obtained in example 5 is attributed to the process of the dibenzo eight-membered ring changing 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 change in length of the epoxy resin obtained in example 5 was observed. As shown in fig. 3, the length of the sample increases and then decreases as the temperature increases, and the length of the sample still decreases until equilibrium when the temperature stays at 100 ℃. This abnormal length change curve is derived from a time-dependent conformational transition process.
The low or negative expansion behavior of the epoxy resins of examples 2-5 results from the process of the dibenzo eight-membered ring conformational transition, which should be accompanied by an energy change. In examples 2 to 5, the obtained epoxy resin had a characteristic endothermic peak in the DSC spectrum (FIG. 4) with 60 ℃ as the origin, which could be attributed to conformational transition.
In addition, temperature-variable infrared testing of the epoxy resin obtained in example 5 can also demonstrate the conformational transition of the benzo-octamembered ring building block that occurs during temperature increase. According to theoretical calculations, intramolecular hydrogen bonds are present in the boat conformation, while the chair conformation does not. As shown in FIG. 5, the-NH-peak (3367 cm) increased with temperature-1) The gradual weakening is narrow, and the rest peaks are almost unchanged, which indicates that the number of hydrogen bonds is reduced, namely the boat conformation is reduced, and the boat conformation is converted into the chair conformation.
Claims (5)
1. The high-performance epoxy resin with the adjustable and controllable thermal expansion coefficient is characterized in that the high-performance epoxy resin is epoxy resin containing dibenzo-eight-membered ring structural units, an aromatic amine curing agent containing dibenzo-eight-membered ring structures is used as a raw material to cure the epoxy resin, 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 specific steps are as follows:
dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove a 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 a high-performance epoxy resin;
the aromatic amine curing agent comprises two components, wherein the first component comprises: the aromatic amine (I) containing dibenzo eight-membered ring structure has the structural formula:
r1 and R2 are any 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) having the general formula:
r is
Any one of the above;
in the curing reaction process, the proportion of the two components in the aromatic amine curing agent is adjusted, 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 adjusted.
2. The high-performance epoxy resin with controllable thermal expansion coefficient as claimed in 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. The preparation method of the high-performance epoxy resin with adjustable and controllable thermal expansion coefficient according to claim 1, which comprises the following steps: dissolving an aromatic amine curing agent and an epoxy resin matrix in N-methyl-2-pyrrolidone, volatilizing to remove a 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.
4. The method according to claim 3, wherein the aromatic amine curing agent is prepared by the following synthetic route:
the method comprises the following specific steps:
(1) adding solvent ultra-dry dichloromethane and 3-5 equivalents of aluminum chloride into a Schlenk tube under anhydrous and anaerobic conditions; stirring for 5-10 minutes at the temperature of-30 to-25 ℃, adding 3-5 equivalents of acetyl chloride and 1 equivalent of dibenzocyclooctane, continuing stirring and reacting for 10-15 hours, and reacting in a nitrogen atmosphere; after the reaction is finished, washing and purifying the reaction solution to obtain an intermediate compound 1;
(2) adding solvent ultra-dry tetrahydrofuran and aluminum chloride into a reaction bottle in an equivalent of 4-6 under the atmosphere of nitrogen, adding 8-12 equivalents of sodium borohydride into the system, and stirring for 10-20 minutes; adding 1 equivalent of the compound 1, and carrying out reflux reaction for 10-15 hours at 40-60 ℃; after the reaction is finished, cooling the system to room temperature, washing and purifying to obtain an intermediate compound 2;
(3) adding 40-60 mL of ultra-dry dichloromethane and 3-5 equivalents of aluminum chloride into a Schlenk tube under anhydrous and anaerobic conditions; after cooling to-25-30 ℃, adding 3-5 equivalent of acetyl chloride into the mixture, and continuously stirring for 5-10 minutes; adding 1 equivalent of the compound 2 into the solution, and continuously stirring and reacting at-25 to-30 ℃ for about 10 to 15 hours; after the reaction is finished, washing and purifying the reaction solution to obtain an intermediate compound 3;
(4) adding 1 equivalent of the compound 3 into a reaction bottle, wherein a solvent is methanol, and placing the reaction bottle in an oil bath kettle at the temperature of 55-60 ℃; then adding 10-20 equivalents of sodium hypochlorite aqueous solution, and continuously stirring for reaction for 8-12 hours; after the reaction is finished, cooling the system to room temperature, and performing suction filtration and purification to obtain an intermediate compound 4;
(5) adding 1 equivalent of compound 4 and a solvent methanol into a round-bottom flask, completely dissolving, adding 8-12 equivalents of sodium hydroxide aqueous solution, and continuously stirring the reaction system at 55-60 ℃ for 10-15 hours; after the reaction is finished, obtaining an intermediate compound 5 through acidification, suction filtration, washing and drying;
(6) dissolving 1 equivalent of the compound 5 in 80-120 equivalents of thionyl chloride, and carrying out reflux reaction at 60-70 ℃ for 10-15 hours; removing thionyl chloride, adding dichloromethane serving as a solvent 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.
5. Use of a high performance epoxy resin with controllable thermal expansion coefficient according to claim 1 in any of the fields of electronic circuit boards, adhesives or packaging materials, or for controlling the thermal expansion behavior of other materials.
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| CN111500046A (en) * | 2020-05-25 | 2020-08-07 | 常州中英科技股份有限公司 | Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and thermosetting copper-clad plate prepared from polyarylether base composition |
| US20210387987A1 (en) * | 2020-06-15 | 2021-12-16 | National Technology & Engineering Solutions Of Sandia, Llc | Crosslinked Polymers with Tunable Coefficients of Thermal Expansion |
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| CN111500046A (en) * | 2020-05-25 | 2020-08-07 | 常州中英科技股份有限公司 | Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and thermosetting copper-clad plate prepared from polyarylether base composition |
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