CN117567725B - Poly (epichlorohydrin) epoxy resin, preparation method thereof and epoxy resin cured product - Google Patents
Poly (epichlorohydrin) epoxy resin, preparation method thereof and epoxy resin cured product Download PDFInfo
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- CN117567725B CN117567725B CN202410051390.9A CN202410051390A CN117567725B CN 117567725 B CN117567725 B CN 117567725B CN 202410051390 A CN202410051390 A CN 202410051390A CN 117567725 B CN117567725 B CN 117567725B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 57
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 57
- 229920002755 poly(epichlorohydrin) Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 6
- 238000003756 stirring Methods 0.000 claims abstract description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000011010 flushing procedure Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 14
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- 150000001642 boronic acid derivatives Chemical class 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 8
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 8
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 8
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 8
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000002901 radioactive waste Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 230000002285 radioactive effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
-
- 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
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
-
- 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
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
-
- 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
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/307—Processing by fixation in stable solid media in polymeric matrix, e.g. resins, tars
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Epoxy Resins (AREA)
Abstract
The patent refers to the field of 'macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds'. Adding dichloroethane, boron trifluoride diethyl etherate solution and ethylene glycol, uniformly stirring, then dropwise adding epichlorohydrin, and heating the reaction solution for reaction; cooling to room temperature, repeatedly flushing with saturated sodium bicarbonate solution and deionized water to neutrality, and evaporating dichloroethane to obtain hydroxyl-terminated polyepichlorohydrin; and (3) dissolving hydroxyl-terminated polyepichlorohydrin in toluene, heating, adding analytically pure NaOH for reaction, adding HCl, repeatedly washing with deionized water to neutrality, and evaporating the toluene to obtain the polyepichlorohydrin epoxy resin. The epoxy resin condensate is prepared from the following raw materials: an epoxy matrix resin, a polyether amine curing agent, which is prepared by mixing a polyepichlorohydrin epoxy resin, an epoxy resin CY-183 and an epoxy resin E-44.
Description
Technical Field
The invention relates to the technical field of radioactive waste treatment, in particular to a polyepichlorohydrin epoxy resin, a preparation method thereof and an epoxy resin condensate.
Background
Radioactive wet waste, including waste resins and radioactive salt blocks. At present, the treatment technology at home and abroad mainly comprises cement curing, polymer curing, thermal super compaction, polymer-filled HIC dehydration, wet oxidation, high-efficiency curing, steam reforming and the like for borates generated by pressurized water reactor operation.
Cement curing, which uses a portland cement substrate as a cured body material of nuclear waste, has been widely used in many countries and has been applied in large-scale engineering in germany, france, america, japan, india, etc. by a method of curing nuclide ions in nuclear waste by mechanical curing, adsorption curing, and chemical curing. The cement solidification has the advantages of simple process, less equipment and operation investment, low energy consumption, safe operation and the like. It has two important drawbacks: the radionuclide leaching rate is high, 2 orders of magnitude higher than that of asphalt curing, and 4-5 orders of magnitude higher than that of glass curing; the volume of the waste after solidification increases much, which is a non-negligible problem in countries and regions where the treatment plants are under tension and the treatment costs are high.
At present, there is no public report of curing by using epoxy resin in China, and the current general method for treating medium-low radioactive waste is cement curing, limited volume reduction and poor performance of a cured body.
Disclosure of Invention
In order to solve the problems of limited volume reduction of low-emissivity borate and poor performance of a cured body in the existing cement curing treatment, the invention provides a polyepichlorohydrin epoxy resin, a preparation method thereof and an epoxy resin cured product.
The technical scheme of the invention is as follows:
a polypropylene oxide epoxy resin has the following structural formula:
，
the epoxy value of the polyepichlorohydrin epoxy resin is 0.12-0.14.
The invention also provides a preparation method of the polyepichlorohydrin epoxy resin, which comprises the following steps:
s1, adding a certain amount of dichloroethane, boron trifluoride diethyl etherate solution and ethylene glycol into a reaction kettle at a first temperature, uniformly stirring, then dropwise adding epichlorohydrin, and heating the reaction solution to a specific temperature after the dropwise adding is finished for reaction;
s2, after the reaction liquid is cooled to room temperature, repeatedly flushing the reaction liquid to be neutral by using saturated sodium bicarbonate solution and deionized water in sequence, and then evaporating dichloroethane to obtain hydroxyl-terminated polyepichlorohydrin;
s3, dissolving the hydroxyl-terminated polyepichlorohydrin in toluene, heating to a reaction temperature, adding analytically pure NaOH, reacting for a certain time, adding HCl solution, neutralizing the rest NaOH, repeatedly washing with deionized water until the solution is neutral, and evaporating the toluene to obtain the hydroxyl-terminated polyepichlorohydrin epoxy resin.
Preferably, in step S1, the first temperature is 18 ℃ to 20 ℃.
Preferably, the specific temperature in step S1 is 40 ℃.
Preferably, the reaction temperature in step S3 is 90 ℃ and the reaction time is 4 hours.
The invention also provides an epoxy resin condensate which is prepared from the following raw materials: (a) an epoxy matrix resin; (b) a polyether amine curing agent;
the epoxy matrix resin is a mixture of polyepichlorohydrin epoxy resin, epoxy resin CY-183 and epoxy resin E-44; wherein the polyepichlorohydrin epoxy resin is the polyepichlorohydrin epoxy resin described above.
Preferably, the mass ratio of the polyepichlorohydrin epoxy resin to the epoxy resin CY-183 to the epoxy resin E-44 is 40-60: 5-15: 25-55.
Preferably, the mass ratio of the epoxy matrix resin to the polyether amine curing agent is 100: 30-45.
Preferably, the polyether amine curing agent has the following structural formula:
wherein n=1 to 3;
the amine value of the polyether amine curing agent is 253 mgKOH/g-465 mgKOH/g.
The preparation method of the polyether amine curing agent comprises the following steps:
s1, adding cardanol and epichlorohydrin into tetrahydrofuran, stirring uniformly at room temperature, then dropwise adding DBU, stirring for a specific time, and then drying;
s2, uniformly mixing 1,2 dichloroethane, propylene glycol and boron trifluoride diethyl etherate at a first temperature, dropwise adding the product prepared in the step S1, continuously stirring, heating the system to a specific temperature, continuously stirring, and ending the reaction;
s3, adding water into the reaction system, layering the solution, extracting, performing rotary evaporation on the oil layer to obtain a yellow viscous product, and adding the yellow viscous product into an amination reactor for ammonification reaction to obtain the aminopolyether curing agent.
The reaction route is as follows:
。
preferably, the mass ratio of cardanol, epichlorohydrin to DBU is 100:500:10; the specific time in the step S1 is 2h; in the step S2, the first temperature is 18-20 ℃, and the specific temperature is 40 ℃; the ratio of ammonia to alcohol in the amination reactor in step S3 is 6.5:1, the catalyst used is Ni catalyst, the initial pressure of hydrogen is 2MPa, the reaction temperature is 230 ℃, and the reaction time is 7h.
The invention also provides application of the epoxy resin cured product, which is particularly applied to curing treatment of the medium-low radioactive borate.
Compared with the prior art, the invention has the following specific beneficial effects:
the borate needs to be uniformly dispersed in a cured body by a matrix resin with larger viscosity, and the polyepichlorohydrin epoxy resin (PECH epoxy resin) provided by the invention is mixed with commercial CY-183 and E-44 to serve as an epoxy matrix resin, the combination of the E-44 and the PECH epoxy resin plays the roles of adjusting viscosity and uniformly dispersing the borate, and meanwhile, the PECH epoxy resin plays the role of toughening, so that the cured body is not easy to crack, the CY-183 plays the role of adjusting the curing speed, and the uniform dispersion of the borate in the cured body is promoted. The epoxy matrix resin and the specific polyether amine curing agent can be crosslinked and cured at room temperature, the obtained cured product has excellent mechanical properties, ageing resistance, fireproof performance and other properties, the cured product is uniform, the inclusion rate is high, the technical index is far higher than the requirements in GB14569.2-1993 Standard of Low and horizontal radioactive waste curing body Performance requirement Plastic curing body, and the epoxy matrix resin and the specific polyether amine curing agent can be applied to the treatment work of medium and low radioactive borates to safely transport and stack and store a large volume of cured body.
Detailed Description
In order to make the technical solution of the present invention more clear, the following description will clearly and completely describe the technical solution of the embodiments of the present invention, and it should be noted that the following embodiments are only used for better understanding the technical solution of the present invention, and should not be construed as limiting the present invention.
Example 1.
Adding dichloroethane, boron trifluoride diethyl etherate solution and ethylene glycol into a reaction kettle at 18-20 ℃, uniformly stirring, then dropwise adding epichlorohydrin, and heating the reaction solution to 40 ℃ for reaction after the dropwise adding is finished;
after the reaction liquid is cooled to room temperature, repeatedly flushing the reaction liquid to be neutral by using saturated sodium bicarbonate solution and deionized water in sequence, and then steaming out dichloroethane to obtain hydroxyl-terminated polyepichlorohydrin;
and (3) dissolving the hydroxyl-terminated polyepichlorohydrin in toluene, heating to 90 ℃, adding analytically pure NaOH to react for 4 hours, adding HCl solution to neutralize the rest NaOH, repeatedly washing with deionized water until the solution is neutral, and then steaming out toluene to obtain the hydroxyl-terminated polyepichlorohydrin epoxy resin.
And (3) carrying out hydrogen spectrum test on the product to obtain nuclear magnetic resonance hydrogen spectrum:
1 HNMR(CDCl 3 ppm):7.26(CDCl 3 )，3.63(3H),3.48(1H),3.38(3H),3.37(2H),2.86(1H)，2.63(1H),2.53(1H),2.38(2H).
example 2.
Uniformly mixing 50 parts of the polyepichlorohydrin epoxy resin prepared in the example 1, 45 parts of E-44 and 5 parts of CY-183, mixing 30 parts of the cardanol modified polyether amine curing agent with the mixture, uniformly stirring the mixture, and removing bubbles in vacuum (-0.1-0.08 MPa) at normal temperature; the method comprises the steps of (1) pouring uniformly mixed materials into a silica gel mold (with the inner diameter of 50mm and the inner height of 52mm, and the height of 35mm when the borates are added) containing borates, slowly stirring the materials in the same direction while pouring, enabling the materials to be fully mixed with a coating at the stirring speed of 0.5-1 rpm, then placing the poured mold in a room temperature environment for curing for 7 days, taking out the cured cylinder from the silica gel mold, and polishing the upper edge of the cylinder to be tested.
Example 3.
Uniformly mixing 50 parts of the polyepichlorohydrin epoxy resin prepared in the example 1, 45 parts of E-44 and 5 parts of CY-183, mixing 35 parts of the cardanol modified polyether amine curing agent with the mixture, uniformly stirring the mixture, and removing bubbles in vacuum (-0.1-0.08 MPa) at normal temperature; the method comprises the steps of (1) pouring uniformly mixed materials into a silica gel mold (with the inner diameter of 50mm and the inner height of 52mm, and the height of 35mm when the borates are added) containing borates, slowly stirring the materials in the same direction while pouring, enabling the materials to be fully mixed with a coating at the stirring speed of 0.5-1 rpm, then placing the poured mold in a room temperature environment for curing for 7 days, taking out the cured cylinder from the silica gel mold, and polishing the upper edge of the cylinder to be tested.
Example 4.
Uniformly mixing 50 parts of the polyepichlorohydrin epoxy resin prepared in the example 1, 45 parts of E-44 and 5 parts of CY-183, mixing 40 parts of the cardanol modified polyether amine curing agent with the mixture, uniformly stirring the mixture, and removing bubbles in vacuum (-0.1-0.08 MPa) at normal temperature; the method comprises the steps of (1) pouring uniformly mixed materials into a silica gel mold (with the inner diameter of 50mm and the inner height of 52mm, and the height of 35mm when the borates are added) containing borates, slowly stirring the materials in the same direction while pouring, enabling the materials to be fully mixed with a coating at the stirring speed of 0.5-1 rpm, then placing the poured mold in a room temperature environment for curing for 7 days, taking out the cured cylinder from the silica gel mold, and polishing the upper edge of the cylinder to be tested.
Example 5.
Uniformly mixing 50 parts of the polyepichlorohydrin epoxy resin prepared in the example 1, 45 parts of E-44 and 5 parts of CY-183, mixing 45 parts of the cardanol modified polyether amine curing agent with the mixture, uniformly stirring the mixture, and removing bubbles in vacuum (-0.1-0.08 MPa) at normal temperature; the method comprises the steps of (1) pouring uniformly mixed materials into a silica gel mold (with the inner diameter of 50mm and the inner height of 52mm, and the height of 35mm when the borates are added) containing borates, slowly stirring the materials in the same direction while pouring, enabling the materials to be fully mixed with a coating at the stirring speed of 0.5-1 rpm, then placing the poured mold in a room temperature environment for curing for 7 days, taking out the cured cylinder from the silica gel mold, and polishing the upper edge of the cylinder to be tested.
Example 6.
Uniformly mixing 60 parts of the polyepichlorohydrin epoxy resin prepared in the example 1, 35 parts of E-44 and 5 parts of CY-183, mixing 35 parts of the cardanol modified polyether amine curing agent with the mixture, uniformly stirring the mixture, and removing bubbles in vacuum (-0.1-0.08 MPa) at normal temperature; the method comprises the steps of (1) pouring uniformly mixed materials into a silica gel mold (with the inner diameter of 50mm and the inner height of 52mm, and the height of 35mm when the borates are added) containing borates, slowly stirring the materials in the same direction while pouring, enabling the materials to be fully mixed with a coating at the stirring speed of 0.5-1 rpm, then placing the poured mold in a room temperature environment for curing for 7 days, taking out the cured cylinder from the silica gel mold, and polishing the upper edge of the cylinder to be tested.
Example 7.
Uniformly mixing 60 parts of the polyepichlorohydrin epoxy resin prepared in the example 1, 35 parts of E-44 and 5 parts of CY-183, mixing 45 parts of the cardanol modified polyether amine curing agent with the mixture, uniformly stirring the mixture, and removing bubbles in vacuum (-0.1-0.08 MPa) at normal temperature; the method comprises the steps of (1) pouring uniformly mixed materials into a silica gel mold (with the inner diameter of 50mm and the inner height of 52mm, and the height of 35mm when the borates are added) containing borates, slowly stirring the materials in the same direction while pouring, enabling the materials to be fully mixed with a coating at the stirring speed of 0.5-1 rpm, then placing the poured mold in a room temperature environment for curing for 7 days, taking out the cured cylinder from the silica gel mold, and polishing the upper edge of the cylinder to be tested.
Effect example.
Performance tests were carried out in accordance with GB14569.2-1993 Standard for Low, horizontal, radioactive waste curing body Performance requirement plastics curing body.
(1) The cured bodies coated with borate prepared in examples 2-7 are respectively subjected to compressive strength tests, and the compressive strength test results of each group are more than 80MPa and far higher than 7 MPa required by national standards;
(2) The cured bodies coated with borate prepared in examples 2-7 were subjected to drop tests from 9m high, and tested for impact resistance, and each group was not damaged after being observed to drop;
(3) The cured bodies coated with borate prepared in examples 2 to 7 were subjected to gamma irradiation at a dose of 1X 106Gy, and after a certain period of irradiation, each group was again tested for compressive strength, and the results are shown in Table 1. Under the condition that the volume inclusion rate of the waste resin is 65%, and after the radiation of a higher dose, the compressive strength of the solidified material is not reduced, but slightly increased;
(4) The anti-freezing-thawing property test is carried out on the cured body coated with borate prepared in the examples 2-7, the volume of the cured body is hardly changed after the test, the reduction rate of compressive strength is not more than 1%, and the performance is far higher than the national standard requirement;
(5) Carrying out a soaking resistance test on the cured body coated with borate prepared in the examples 2-7, wherein the cured body is not broken after the test, and the volume change rate and the compressive strength change rate meet the standard requirements;
(6) The borate-coated cured bodies prepared in examples 2 to 7 were tested for flame retardancy, self-extinguishing in 30 seconds after the fire source was removed, leaving a carbonized layer of only 1mm in thickness on the surface of the cured body, with a mass loss of not more than 12%, and meeting the requirements.
TABLE 1
The test results show that the technical index of the epoxy resin cured product provided by the application is far higher than the requirements in GB14569.2-1993 'Low and horizontal radioactive waste cured body performance requirement plastic cured body', the mechanical property is excellent, the ageing resistance and the fireproof property are excellent, and the epoxy resin cured product can be applied to the treatment work of medium and low radioactive waste resin to safely transport and stack and store a large volume of cured body, so that the danger of nuclear leakage is avoided.
Claims (5)
1. An epoxy resin condensate is characterized by being prepared from the following raw materials: (a) an epoxy matrix resin; (b) a polyether amine curing agent;
the epoxy matrix resin is a mixture of polyepichlorohydrin epoxy resin, epoxy resin CY-183 and epoxy resin E-44;
the structural formula of the polyepichlorohydrin epoxy resin is as follows:
；
the epoxy value of the polyepichlorohydrin epoxy resin is 0.12-0.14;
the structural general formula of the polyether amine curing agent is as follows:
wherein n=1 to 3;
the amine value of the polyether amine curing agent is 253 mgKOH/g-465 mgKOH/g;
the mass ratio of the polyepichlorohydrin epoxy resin to the epoxy resin CY-183 to the epoxy resin E-44 is 40-60: 5-15: 25-55.
2. The epoxy resin cured product according to claim 1, wherein the mass ratio of the epoxy base resin to the polyether amine curing agent is 100: 30-45.
3. The cured epoxy resin of claim 1, wherein the polyepichlorohydrin epoxy resin is prepared by:
s1, adding dichloroethane, boron trifluoride diethyl etherate solution and ethylene glycol into a reaction kettle at 18-20 ℃, uniformly stirring, then dropwise adding epichlorohydrin, and heating the reaction solution to 40 ℃ for reaction after the dropwise adding is finished;
s2, after the reaction liquid is cooled to room temperature, repeatedly flushing the reaction liquid to be neutral by using saturated sodium bicarbonate solution and deionized water in sequence, and then evaporating dichloroethane to obtain hydroxyl-terminated polyepichlorohydrin;
s3, dissolving the hydroxyl-terminated polyepichlorohydrin in toluene, heating to a reaction temperature, adding analytically pure NaOH, reacting for a certain time, adding HCl solution, neutralizing the rest NaOH, repeatedly washing with deionized water until the solution is neutral, and evaporating the toluene to obtain the hydroxyl-terminated polyepichlorohydrin epoxy resin.
4. The cured epoxy resin of claim 3, wherein the reaction temperature in step S3 is 90 ℃ and the reaction time is 4 hours.
5. The use of the cured epoxy resin according to any one of claims 1 to 4, wherein the cured epoxy resin is used for curing a borate with a medium or low radioactivity.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1596783A (en) * | 1978-03-21 | 1981-08-26 | Europ Pour Le Traitement Chimi | Treatment of radioactive waste |
| CN107722239A (en) * | 2017-10-24 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of epoxide resin material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1596783A (en) * | 1978-03-21 | 1981-08-26 | Europ Pour Le Traitement Chimi | Treatment of radioactive waste |
| CN107722239A (en) * | 2017-10-24 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of epoxide resin material and preparation method thereof |
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