CN114524785A - High-purity high-thermal-stability alicyclic epoxy resin monomer and preparation method thereof - Google Patents
High-purity high-thermal-stability alicyclic epoxy resin monomer and preparation method thereof Download PDFInfo
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- CN114524785A CN114524785A CN202210075544.9A CN202210075544A CN114524785A CN 114524785 A CN114524785 A CN 114524785A CN 202210075544 A CN202210075544 A CN 202210075544A CN 114524785 A CN114524785 A CN 114524785A
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- 239000000178 monomer Substances 0.000 title claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 24
- 125000002723 alicyclic group Chemical group 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 7-oxabicyclo [4.1.0] heptyl-3-yl Chemical group 0.000 claims abstract description 16
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- QBJOHGAEIAUULA-UHFFFAOYSA-N cyclohexen-1-ylmethanol Chemical compound OCC1=CCCCC1 QBJOHGAEIAUULA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- 238000006467 substitution reaction Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 14
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 4
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 claims 1
- JMTOWIGWAQDRBE-UHFFFAOYSA-N cyclohexene;methanol Chemical compound OC.C1CCC=CC1 JMTOWIGWAQDRBE-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011810 insulating material Substances 0.000 abstract description 7
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000001723 curing Methods 0.000 description 4
- BSIUOOFOIGCVSG-UHFFFAOYSA-N 3-[6-(7-oxabicyclo[4.1.0]heptan-3-ylmethoxy)hexoxymethyl]-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1COCCCCCCOCC1CC2OC2CC1 BSIUOOFOIGCVSG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
-
- 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
- C08G59/22—Di-epoxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a high-purity high-thermal-stability alicyclic epoxy resin monomer and a preparation method thereof, which are characterized in that cyclohexene methanol and 1, 6-dibromohexane are used as raw materials, substitution reaction is carried out to obtain 1, 6-bis (cyclohexyl-3-alkene-1-methoxyl) hexane, and cyclization reaction is carried out with dichloroethane to obtain the high-purity high-thermal-stability alicyclic epoxy resin monomer. The 1, 6-bis ((7-oxabicyclo [4.1.0] heptyl-3-yl) methoxyl) hexane is more stable than ERL4299, and application finds that the 1, 6-bis ((7-oxabicyclo [4.1.0] heptyl-3-yl) methoxyl) hexane is excellent in weather resistance, does not crack or yellow, generates carbon dioxide and water during electric decomposition, is particularly suitable for insulating materials with high requirements on electric properties, and is good in high-temperature insulation property and strong in arc resistance and leakage resistance.
Description
Technical Field
The invention belongs to a preparation technology of an epoxy resin monomer, and particularly relates to a high-purity high-thermal-stability alicyclic epoxy resin monomer and a preparation method thereof.
Background
Bis ((3, 4-epoxycyclohexyl) methyl) adipate (ERL4299) is a special functional epoxy resin developed by united states carbon chemical company and has the following characteristics: the saturated structure is excellent in weather resistance, the finished product is not cracked or yellowed, carbon dioxide and water are generated during electric decomposition, and short circuit caused by graphite generated by aromatic resin is avoided; the chlorine content is low, the insulating material with high requirement on electrical performance is particularly suitable, the high-temperature insulating property is good, and the arc resistance and the electric leakage resistance are strong; but the product cannot be used in some special application scenes due to the structural particularity. Therefore, the development of new epoxy resin monomers is needed to improve the stability and viscosity characteristics of ERL 4299.
Disclosure of Invention
Compared with ERL4299, the light-cured epoxy resin with low viscosity and high toughness developed by the invention has more stable performance.
A high purity high thermal stability cycloaliphatic epoxy resin monomer having the chemical name 1, 6-bis ((7-oxabicyclo [4.1.0] heptan-3-yl) methoxy) hexane and the chemical formula:
the invention discloses a preparation method of the high-purity high-thermal stability alicyclic epoxy resin monomer, which comprises the steps of taking cyclohexene methanol and 1, 6-dibromohexane as raw materials, carrying out substitution reaction to obtain 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane, and carrying out cyclization reaction with dichloroethane to obtain the high-purity high-thermal stability alicyclic epoxy resin monomer; preferably, the temperature of the substitution reaction is 70-90 ℃, preferably 80 ℃, and the time is 3-5 hours, preferably 4 hours; the temperature of the cyclization reaction is 10-15 ℃, and the time is 4-6 h.
In the invention, the substitution reaction is carried out in an organic solvent in the presence of tetrabutylammonium bromide and potassium hydroxide; after the reaction is finished, adding water and an organic solvent, adjusting the pH value to 5-6, carrying out phase separation, washing the organic phase with water, removing the solvent, and carrying out reduced pressure distillation to obtain 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane; the organic solvent is preferably toluene.
In the present invention, the cyclization reaction is carried out in the presence of sodium carbonate, DPN (sodium polyphosphate), peroxyacetic acid; and after the reaction is finished, standing and separating liquid, taking the upper layer solution, washing with water, washing with alkali, and removing the solvent to obtain the high-purity high-thermal-stability alicyclic epoxy resin monomer.
The bis ((3, 4-epoxycyclohexyl) methyl) adipate (ERL4299) has a saturated structure, is excellent in weather resistance, does not crack or yellow, generates carbon dioxide and water during electrical decomposition, does not cause short circuit unlike graphite generated by aromatic resin, is low in chlorine content, is particularly suitable for insulating materials with high requirements on electrical properties, and is good in high-temperature insulation property, arc-resistant and tracking-resistant; but the viscosity is larger and the thermal stability is lower, the invention discloses a novel epoxy monomer structure, and the epoxy resin has better thermal stability and low viscosity while being suitable for the application of electric insulating materials.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectra of a product of example one.
Detailed Description
The raw materials of the invention are the existing products, DPN (sodium polyphosphate) is the Chinese medicine product; the specific preparation operation and test method are the prior art. The preparation process route of the high-purity high-thermal-stability alicyclic epoxy resin monomer is as follows:
example one
Adding 53.76g (0.1mol) of cyclohexene methanol into a 500mL reaction bottle, adding 86.6g of toluene as a solvent, adding 2g of tetrabutylammonium bromide, 40.4g of potassium hydroxide and 48.76g of 1, 6-dibromohexane under conventional stirring, controlling the temperature to be 80 ℃, reacting for 4 hours, then naturally cooling to room temperature, adding 86.6g of water and 86.6g of toluene into the system, dropwise adding 35mL of concentrated hydrochloric acid to adjust the pH value to be 5, standing, carrying out phase separation, washing an organic phase for 2 times, concentrating, carrying out desolventization, and carrying out reduced pressure distillation at 190 ℃ to obtain 28g of 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane with the yield of 63.9%.
Adding 100g (0.62mol) of 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane into a 1000mL reaction flask, adding 300g of dichloroethane, 8.72g (0.08mol) of sodium carbonate and 0.072g of DPN, reducing the temperature in the reaction flask to 10 ℃ under conventional stirring, dropwise adding 152g (2.24mol) of 23 wt% peroxyacetic acid solution, reacting for 6 hours after 10 minutes of dropwise addition, standing, separating, washing the organic phase with 100g of water for 2 times, washing the organic phase with 100g of 10 wt% NaOH aqueous solution once, washing with 100g of water for 2 times, decompressing, desolventizing, and collecting the product 1, 6-bis ((7-oxabicyclo [ 4.1.0)]Heptan-3-yl) methoxy) hexane 107g (0.53mol), yield 85.5%, NMR chart shown in FIG. 1:1H NMR(400MHz,CDCl3)δ3.43-3.26(m,4H),3.25-2.87(m,8H),2.20-1.90(m,4H),1.87-1.65(m,3H),1.62-1.37(m,9H),1.36-1.18(m,4H),1.18-0.84(m,2H)。
example two
Adding 53.76g (0.1mol) of cyclohexene methanol into a 500mL reaction bottle, adding 86.6g of toluene as a solvent, adding 2g of tetrabutylammonium bromide, 40.4g of potassium hydroxide and 48.76g of 1, 6-dibromohexane under conventional stirring, controlling the temperature to be 80 ℃, reacting for 3.5h, then naturally cooling to room temperature, adding 86.6g of water and 86.6g of toluene into the system, dropwise adding concentrated hydrochloric acid to adjust the pH value to be 6, standing, phase-splitting, washing an organic phase for 2 times, concentrating, desolventizing, and distilling at 190 ℃ under reduced pressure to obtain 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane with the yield of 62.2%; 100g (0.62mol) of 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane was charged into a 1000mL reaction flask, 300g of dichloroethane, 8.72g (0.08mol) of sodium carbonate and 0.072g of DPN were added, the temperature in the reaction flask was lowered to 15 ℃ under ordinary stirring, 152g (2.24mol) of a 23 wt% peracetic acid solution was added dropwise, after completion of the reaction for 10 minutes, the reaction was left to stand for liquid separation, the organic phase was washed with 100g of water for 2 times, then washed with 100g of a 10 wt% aqueous NaOH solution once, and after washing with 100g of water for 2 times, the solution was desolventized under reduced pressure to obtain 1, 6-bis ((7-oxabicyclo [4.1.0] heptane-3-yl) methoxy) hexane in 83.9% yield.
EXAMPLE III
Adding 53.76g (0.1mol) of cyclohexene methanol into a 500mL reaction bottle, adding 86.6g of toluene as a solvent, adding 2g of tetrabutylammonium bromide, 28.8g of sodium hydroxide and 48.76g of 1, 6-dibromohexane under conventional stirring, controlling the temperature to be 80 ℃, reacting for 4 hours, then naturally cooling to room temperature, adding 86.6g of water and 86.6g of toluene into the system, dropwise adding concentrated hydrochloric acid to adjust the pH value to be 5, standing, carrying out phase separation, washing an organic phase for 2 times, concentrating, removing solvent, carrying out reduced pressure distillation at 190 ℃ to obtain the 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane with the yield of 52.6%.
100g (0.62mol) of 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane was charged into a 1000mL reaction flask, 300g of dichloroethane, 11.06g (0.08mol) of potassium carbonate and 0.072g of DPN were added, the temperature in the reaction flask was lowered to 10 ℃ under ordinary stirring, 152g (2.24mol) of a 23 wt% peracetic acid solution was added dropwise, after completion of the reaction for 10 minutes, followed by reaction for 6 hours, standing and liquid separation, the organic phase was washed with 100g of water for 2 times, then washed with 100g of a 10 wt% aqueous NaOH solution once, and after washing with 100g of water for 2 times, desolvation was carried out under reduced pressure to obtain 1, 6-bis ((7-oxabicyclo [4.1.0] heptane-3-yl) methoxy) hexane as a product with a yield of 75.3%.
Comparative example one omission of tetrabutylammonium bromide
Cyclohexene methanol 53.76g (0.1mol) is added into a 500mL reaction bottle, 86.6g toluene is added as a solvent, 40.4g potassium hydroxide and 48.76g1, 6-dibromohexane are added under the conventional stirring condition, the temperature is controlled to be 80 ℃, the reaction is carried out for 4h, then the reaction is naturally cooled to the room temperature, and sampling GC detects that 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane is not found.
Application examples
The viscosity test method is GB/T22314-2008, and the low viscosity of the target product is beneficial to blending and curing with other materials.
ERL4299 structure:
100 parts of epoxy monomer and 0.5 part of T-188 (cation curing agent, east China chemical industry) are mixed for thermal curing, the curing condition is 20 ℃/min, the temperature is raised from 40 ℃ to 250 ℃ and is kept for 0.5 hour, and the result is as follows:
from a comparison of the properties of 1, 6-bis ((7-oxabicyclo [4.1.0] heptyl-3-yl) methoxy) hexane after cationic curing under the same conditions as bis ((3, 4-epoxycyclohexyl) methyl) adipate, it can be seen that 1, 6-bis ((7-oxabicyclo [4.1.0] heptyl-3-yl) methoxy) hexane is more stable than ERL 4299. The application finds that the 1, 6-bis ((7-oxabicyclo [4.1.0] heptyl-3-yl) methoxyl) hexane has excellent weather resistance, the finished product does not crack or yellow, carbon dioxide and water are generated during electric decomposition, the insulating material is particularly suitable for insulating materials with high requirements on electric performance, and the insulating material has good high-temperature insulation property and strong arc resistance and leakage resistance.
Claims (10)
1. A high-purity high-thermal-stability alicyclic epoxy resin monomer is characterized in that the chemical structural formula is as follows:
2. the method for preparing high-purity high-thermal-stability alicyclic epoxy resin monomer according to claim 1, wherein cyclohexene methanol and 1, 6-dibromohexane are used as raw materials, and are subjected to substitution reaction to obtain 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane, and then subjected to cyclization reaction with dichloroethane to obtain high-purity high-thermal-stability alicyclic epoxy resin monomer.
3. The method for preparing a high-purity high-thermal stability alicyclic epoxy resin monomer according to claim 2, wherein the temperature of the substitution reaction is 70 to 90 ℃ for 3 to 5 hours.
4. The method for preparing a high-purity high-thermal stability alicyclic epoxy resin monomer according to claim 2, wherein the temperature of the cyclization reaction is 10 to 15 ℃ and the time is 4 to 6 hours.
5. The method for preparing a high-purity high-thermal-stability alicyclic epoxy resin monomer according to claim 2, wherein the substitution reaction is carried out in an organic solvent in the presence of tetrabutylammonium bromide or a hydroxide; after the reaction is finished, adding water and an organic solvent, adjusting the pH value to 5-6, carrying out phase separation, washing the organic phase with water, removing the solvent, and carrying out reduced pressure distillation to obtain the 1, 6-bis (cyclohex-3-en-1-ylmethoxy) hexane.
6. The method of claim 5, wherein the organic solvent is toluene.
7. The method for producing a high-purity high-thermal-stability alicyclic epoxy resin monomer according to claim 2, wherein the cyclization reaction is carried out in the presence of a carbonate, DPN, peroxyacetic acid; and after the reaction is finished, standing and separating liquid, taking the upper layer solution, washing with water, washing with alkali, and removing the solvent to obtain the high-purity high-thermal-stability alicyclic epoxy resin monomer.
8. The use of cyclohexene carbinol, 1, 6-dibromohexane and dichloroethane as starting materials in the preparation of high purity, high thermal stability cycloaliphatic epoxy resin monomers as claimed in claim 1.
9. Use of the high purity high thermal stability cycloaliphatic epoxy resin monomer of claim 1 in the replacement of bis ((3, 4-epoxycyclohexyl) methyl) adipate.
10. The use according to claim 9, wherein the high-purity high-thermal-stability alicyclic epoxy resin monomer according to claim 1 is used as a raw material for a cured epoxy resin in place of bis ((3, 4-epoxycyclohexyl) methyl) adipate.
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|---|---|---|---|---|
| GB996064A (en) * | 1960-08-24 | 1965-06-23 | Union Carbide Corp | Improvements in and relating to epoxy resins |
| CN1659204A (en) * | 2002-06-06 | 2005-08-24 | 亨斯迈先进材料（瑞士）有限公司 | Actinic radiation curable compositions and their use |
| CN104345562A (en) * | 2013-08-09 | 2015-02-11 | 帝斯曼知识产权资产管理有限公司 | Low-viscosity liquid radiation curable dental aligner mold resin compositions for additive manufacturing |
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