CN107722239A - A kind of epoxide resin material and preparation method thereof - Google Patents
A kind of epoxide resin material and preparation method thereof Download PDFInfo
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- CN107722239A CN107722239A CN201711000492.4A CN201711000492A CN107722239A CN 107722239 A CN107722239 A CN 107722239A CN 201711000492 A CN201711000492 A CN 201711000492A CN 107722239 A CN107722239 A CN 107722239A
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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
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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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- Epoxy Resins (AREA)
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Abstract
The invention provides a kind of epoxide resin material and preparation method thereof, epoxide resin material is made by the raw material including following parts by weight：100 parts of epoxy resin composition；10~20 parts of the CNT base iron-based imidazole ion liquid with the structure of formula II；10~20 parts of amine terminated polyether；Epoxy resin composition includes bisphenol A diglycidyl ether, has the endurable active toughener and the dicarboxylic acid diglycidyl ester of 4,5 oxepane 1,2 of structure shown in formula I.The epoxide resin material has good mechanical performance and anti-leaching performance.Irradiation dose 106Afterwards, compression strength 20MPa, 10m high perpendicular drop to mattess and do not produce obvious fragmentation；Volume Changes are less than 1% after freezing-thawing test, and compression strength, which reduces, is less than 10%；Volumetric expansion is less than 2%；Related nuclide leaching rate is limited to Cs within 42nd day+＜ 5 × 10‑4cm/d、Co2+＜ 1 × 10‑4cm/d。
Description
Technical field
The present invention relates to Epoxy Resin Technology field, more particularly to a kind of epoxide resin material and preparation method thereof.
Background technology
The development and utilization of nuclear energy brings huge economic benefit and social benefit to the mankind, while also generates substantial amounts of
Radwaste, the living environment to the mankind bring larger threat.Therefore, how Spent Radioactive is safely and effectively disposed
Thing, it is set to isolate to greatest extent with biosphere, it has also become the increasingly urgent important topic that nuclear industry, nuclear science face, to be
Influence the key factor of nuclear energy sustainable and healthy development.Disposal to radwaste, it is believed that most rational measure is first
Radwaste is subjected to curing process, then obtained solidification of radwaste body is carried out to final geological disposal.To putting
Injectivity waste, which carries out effective curing process, can reach 3 purposes：It is easy to pacify first, being transformed into the radioactive substance of liquid
Defeated, storage for the national games and the firming body of disposal operations；Second, radionuclide is consolidated, stop that radionuclide enters human biological
Circle；Third, reduce the volume of waste.The solidification of radwaste processing method to have grown up has a lot, the low radiation in
Property waste, mainly there is cement solidification, bitumen solidification and plastics solidification；For high-level waste, mainly have glass solidification and
Extremely potential prosthetic graft solidification now.In terms of the curing process of radwaste, cement solidification technological development is most
It is early, the existing history of more than 40 years so far.Cement solidification has been a kind of ripe technology, by the nuclear power station of many countries, core work
Industry department and Nuclear research centre are widely used, have large-scale engineering application in Germany, France, the U.S., Japan, India etc..
The Qinshan nuclear power plant in China, Daya Bay nuclear power plant etc. all employ cement solidification technique to handle.At present using cement-based solidified
Waste be mainly light water reactor concentrating spent liquor, waste ion-exchang resin and filter residue, and nuclear fuel.With cement solidification
Compare, polymer solidification has the advantage that:1. nuclide leaching rate is relatively low, more lower slightly than bitumen solidification, 2~4 lower than cement solidification
The order of magnitude, this is to realizing that long-term safety isolates important in inhibiting；2. containing, amount of waste is higher, and cured article quantity is few, disposal
Expense is reduced.In the polymer, epoxy resin has preferable radiation-resistant property, therefore can be as the base of solidification of radwaste
Body resin uses.But the domestic engineering example currently without epoxy resin cure radwaste.
Had the disadvantage that at present during general purpose epoxy resin processing radioactive wet waste (spent resin, radioactivity salt block)：(1)
Room-temperature curing epoxy mechanical performance deficiency, the anti-leaching performance after (2) material is irradiated are difficult to reach GB14569.2-1993
《Low, middle level radioactive waste firming body performance requirement plastics solidification body》Related request in standard.
The content of the invention
In view of this, it is an object of the invention to provide a kind of epoxide resin material and preparation method thereof, the epoxy resin
There is good mechanical performance and anti-leaching after material irradiation.
The invention provides a kind of epoxide resin material, is made by the raw material including following parts by weight of component：
100 parts of epoxy resin composition；
10~20 parts of CNT base iron-based imidazole ion liquid；
10~20 parts of amine terminated polyether；
The epoxy resin composition includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepanes -1,2-
Dicarboxylic acid diglycidyl ester；The endurable active toughener has structure shown in formula I：
N=1~10；
The CNT base iron-based imidazole ion liquid has the structure of formula II：
The R is selected from-CH3,-C4H9,-C6H13Or-C11H23。
Preferably, the bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- dioctyl phthalate two contract
The mass ratio of water glyceride is 100:25~40:10~15.
Preferably, the amine terminated polyether is in model D-230, D-200, T-403 and T-5000 amine terminated polyether
One or more.
Preferably, the endurable active toughener obtains epoxide number as 0.12~0.14.
Preferably, the bisphenol A diglycidyl ether is selected from model E-51 bisphenol A diglycidyl ethers；The 4,5-
Oxepane -1,2- dicarboxylic acid diglycidyl esters are shunk selected from model TDE-85 4,5- oxepane -1,2- dioctyl phthalate two
Glyceride.
Preferably, the endurable active toughener is made by following methods：
A) after mixing dichloroethanes, boron trifluoride ether solution and ethylene glycol, epoxychloropropane is added dropwise, reaction, obtains
To reaction solution rinse to neutrality, then steam dichloroethanes, obtain Based On Hydroxy-terminated Polyepichlorohydrin；
B) toluene solution of Based On Hydroxy-terminated Polyepichlorohydrin and NaOH are reacted, obtained reaction solution is neutralized, washing, then
Toluene is steamed, obtains endurable active toughener.
Preferably, the temperature of reaction is 38~42 DEG C in the step a)；The time of reaction is 55~65min；
The temperature of reaction is 85~95 DEG C in the step b)；The time of reaction is 3.5~4.5h.
Preferably, the CNT base iron-based imidazole ion liquid is made by following methods：
A) 1- alkyl imidazoles and chloromethanes are reacted, obtains 1- alkyl -3- methylimidazole villaumite ionic liquids；The 1- alkane
Alkyl is selected from methyl, butyl, hexyl or undecyl in base imidazoles；By 1- alkyl -3- methylimidazole villaumites ionic liquid and three
Iron chloride reacts, and obtains iron-based imidazole ion liquid；
B) in the presence of dimethylformamide, dicyclohexylcarbodiimide and DMAP, carboxyl carbon is received
Mitron and the reaction of iron-based imidazole ion liquid, obtain CNT base iron-based imidazole ion liquid.
Preferably, the temperature of carboxyl CNT and iron-based the imidazole ion liquid reaction is 55~65 DEG C；Carboxyl carbon
The time of nanotube and the reaction of iron-based imidazole ion liquid is 22~26h.
The invention provides a kind of preparation method of epoxide resin material described in above-mentioned technical proposal, comprise the following steps：
By 100 parts of epoxy resin composition, 10~20 parts of CNT base iron-based imidazole ion liquid and amine terminated polyether
10~20 parts of mixing, solidification, obtain epoxide resin material.
The invention provides a kind of epoxide resin material, is made by the raw material including following parts by weight of component：Epoxy resin
100 parts of mixture；10~20 parts of CNT base iron-based imidazole ion liquid；10~20 parts of amine terminated polyether；The asphalt mixtures modified by epoxy resin
Lipoprotein mixture includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- dioctyl phthalate 2-glycidyls
Ester；The endurable active toughener has structure shown in formula I；The CNT base iron-based imidazole ion liquid has the structure of formula II.This hair
The epoxide resin material of bright offer makes it have good mechanical performance and anti-leaching after irradiation under the compatibility of said components
Performance.Test result indicates that：Irradiation dose 106Afterwards, compression strength (reduces degree and is less than 10%) for 20MPa, 10m high perpendiculars
Drop to mattess and do not produce obvious fragmentation；After freeze-thaw experiment, Volume Changes are less than 1%, are visible by naked eyes crack, resist
Compressive Strength, which reduces, is less than 10%；Volumetric expansion is less than 2%；Sample leaches in 25 DEG C of deionized waters, related nucleic leaching in the 42nd day
Extracting rate is limited to Cs+＜ 5 × 10-4cm/d、Co2+＜ 1 × 10-4cm/d。
Embodiment
The invention provides a kind of epoxide resin material, is made by the raw material including following parts by weight of component：
100 parts of epoxy resin composition；
10~20 parts of CNT base iron-based imidazole ion liquid；
10~20 parts of amine terminated polyether；
The epoxy resin composition includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepanes -1,2-
Dicarboxylic acid diglycidyl ester；The endurable active toughener has structure shown in formula I：
N=1~10；
The CNT base iron-based imidazole ion liquid has the structure of formula II：
The R is selected from-CH3,-C4H9,-C6H13Or-C11H23。
Epoxide resin material provided by the invention makes it have good machinery after irradiation under the compatibility of said components
Performance and anti-leaching performance.
In terms of parts by weight, the preparing raw material of epoxide resin material provided by the invention includes epoxy resin composition 100
Part；The epoxy resin composition includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- diformazans
Sour 2-glycidyl ester；The bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- dioctyl phthalate two contract
The mass ratio of water glyceride is preferably 100:25~40:10~15；In specific embodiment of the invention, the epoxy resin mixes
Compound includes the matter of bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters
Amount is than being 100:30:10；100:40:10；Or 100:25:10.The bisphenol A diglycidyl ether is preferably selected from model E-51
Bisphenol A diglycidyl ether；4,5- oxepanes -1,2- the dicarboxylic acid diglycidyl esters are preferably selected from model TDE-85
4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters.
The present invention is to the bisphenol A diglycidyl ether and 4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters
Source does not have special to limit, it is preferred to use its commercial goods.
In the present invention, it is preferably 0.12~0.14 that the endurable active toughener, which obtains epoxide number,.The endurable active toughener is preferred
It is made by following methods：
A) after mixing dichloroethanes, boron trifluoride ether solution and ethylene glycol, epoxychloropropane is added dropwise, reaction, obtains
To reaction solution rinse to neutrality, then steam dichloroethanes, obtain Based On Hydroxy-terminated Polyepichlorohydrin；
B) toluene solution of Based On Hydroxy-terminated Polyepichlorohydrin and NaOH are reacted, obtained reaction solution is neutralized, washing, then
Toluene is steamed, obtains endurable active toughener.
After the present invention mixes dichloroethanes, boron trifluoride ether solution and ethylene glycol, epoxychloropropane is added dropwise, instead
Should, obtained reaction solution is rinsed to neutrality, then steams dichloroethanes, obtains Based On Hydroxy-terminated Polyepichlorohydrin.Epoxy chloropropionate is added dropwise
System temperature is 18~23 DEG C during alkane；System is warming up to 38~42 DEG C after being added dropwise and reacted by epoxychloropropane.At this
In invention, the temperature of reaction is preferably 38~42 DEG C in the step a), more preferably 40 DEG C；The time of reaction is preferably 55~
65min, more preferably 60min.After obtained reaction solution is preferably cooled to room temperature by the present invention, using saturated sodium bicarbonate solution
With deionized water rinsing to neutrality.
After obtaining Based On Hydroxy-terminated Polyepichlorohydrin, the present invention is anti-by the toluene solution and NaOH of Based On Hydroxy-terminated Polyepichlorohydrin
Should, obtained reaction solution is neutralized, washing, then toluene is steamed, obtain endurable active toughener.The present invention is by terminal hydroxy group polycyclic oxygen chlorine
Propane is dissolved in toluene, and NaOH is added after system is warming up into 85~95 DEG C and is reacted, more preferably 90 DEG C；The time of reaction is excellent
Elect 3.5~4.5h, more preferably 4h as.The present invention is preferably added to HCl solution and neutralizes remaining NaOH.
The preparing raw material of epoxide resin material provided by the invention include CNT base iron-based imidazole ion liquid 10~
20 parts.The CNT base iron-based imidazole ion liquid has the structure of formula II：
The R is selected from-CH3,-C4H9,-C6H13Or-C11H23。
In the present invention, the CNT base iron-based imidazole ion liquid is preferably made by following methods：
A) 1- alkyl imidazoles and chloromethanes are reacted, obtains 1- alkyl -3- methylimidazole villaumite ionic liquids；The 1- alkane
Alkyl is selected from methyl, butyl, hexyl or undecyl in base imidazoles；By 1- alkyl -3- methylimidazole villaumites ionic liquid and three
Iron chloride reacts, and obtains iron-based imidazole ion liquid；
B) in the presence of dimethylformamide, dicyclohexylcarbodiimide (DCC) and DMAP (DMAP),
Carboxyl CNT and iron-based imidazole ion liquid are reacted, obtain CNT base iron-based imidazole ion liquid.
In the present invention, the synthetic route of the iron-based imidazole ion liquid is as shown in reaction scheme 1：
In reaction scheme 1, the R is-CH3,-C4H9,-C6H13Or-C11H23。
The present invention does not have special limitation to the source of the carboxyl CNT, and use is well known to those skilled in the art
Carboxyl CNT.In the present invention, the carboxyl CNT is preferably prepared in accordance with the following methods：
CNT and sulfonitric nitration mixture are mixed, ultrasound, back flow reaction, with poly- after reaction product and water are mixed
It is about 7 that tetrafluoroethylene, which is filtered to the pH value of filtrate, obtains carboxyl CNT.
In the present invention, the temperature of carboxyl CNT and iron-based the imidazole ion liquid reaction is preferably 55~65
DEG C, more preferably 58~62 DEG C, most preferably 60 DEG C；The time of carboxyl CNT and the reaction of iron-based imidazole ion liquid is preferred
For 22~26h, more preferably 23h~15h, most preferably 24h.
After the product that carboxyl CNT and iron-based imidazole ion liquid react is centrifugally separating to obtain crude product by the present invention,
Crude product is repeatedly washed with acetonitrile and is centrifuged off the impurity such as redundance, is finally placed in vacuum drying oven and dries, obtain
To CNT base iron-based imidazole ion liquid.
In the specific embodiment of the invention, the synthetic route such as reaction scheme 2 of CNT base iron-based imidazole ion liquid
It is shown：
The preparing raw material of epoxide resin material provided by the invention includes 10~20 parts of amine terminated polyether.In the present invention,
The amine terminated polyether is preferably selected from one kind or more in model D-230, D-200, T-403 and T-5000 amine terminated polyether
Kind.The amine terminated polyether of model described above is produced by red Pola Group Plc.
The invention provides a kind of preparation method of epoxide resin material described in above-mentioned technical proposal, comprise the following steps：
By 100 parts of epoxy resin composition, 10~20 parts of CNT base iron-based imidazole ion liquid and amine terminated polyether
10~20 parts of mixing, solidification, obtain epoxide resin material.
The present invention preferably mixes epoxy resin composition, CNT base iron-based imidazole ion liquid and amine terminated polyether
Removing bubble after uniformly.In the present invention, the temperature of the solidification is preferably 20~25 DEG C.
The invention provides a kind of epoxide resin material, is made by the raw material including following parts by weight of component：Epoxy resin
100 parts of mixture；10~20 parts of CNT base iron-based imidazole ion liquid；10~20 parts of amine terminated polyether；The asphalt mixtures modified by epoxy resin
Lipoprotein mixture includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- dioctyl phthalate 2-glycidyls
Ester；The endurable active toughener has structure shown in formula I；The CNT base iron-based imidazole ion liquid has the structure of formula II.This hair
The epoxide resin material of bright offer makes it have good mechanical performance and anti-leaching after irradiation under the compatibility of said components
Performance.Test result indicates that：Irradiation dose 106Afterwards, compression strength (reduces degree and is less than 10%) for 20MPa, 10m high perpendiculars
Drop to mattess and do not produce obvious fragmentation；After freeze-thaw experiment, Volume Changes are less than 1%, are visible by naked eyes crack, resist
Compressive Strength, which reduces, is less than 10%；Volumetric expansion is less than 2%；Sample leaches in 25 DEG C of deionized waters, related nucleic leaching in the 42nd day
Extracting rate is limited to Cs+＜ 5 × 10-4cm/d、Co2+＜ 1 × 10-4cm/d。
In order to further illustrate the present invention, with reference to embodiment to a kind of epoxide resin material provided by the invention and its
Preparation method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
A certain amount of dichloroethanes, boron trifluoride ether solution and ethylene glycol are added in a kettle, after stirring,
Start that epoxychloropropane is added dropwise, whole reaction temperature control is at 18-23 DEG C.After epoxychloropropane is added dropwise, by reaction solution
40 DEG C are warming up to, reacts a hour.After question response liquid is cooled to room temperature, with saturated sodium bicarbonate solution and deionized water by its
Rinse repeatedly to neutrality, then be Based On Hydroxy-terminated Polyepichlorohydrin (PECH) after dichloroethanes is steamed.Homemade PECH is molten
In appropriate toluene, a certain amount of pure NaOH of analysis is added after being warming up to 90 DEG C, after reacting four hours, it is molten to add HCl/water
Liquid neutralizes remaining NaOH, is washed repeatedly with deionized water until solution is in neutrality, then is epoxy A after toluene is steamed, ring
Oxygen value is 0.12；
The chloromethanes newly distilled is added dropwise into 1- methylimidazoles, is reacted under 60 DEG C of condition of heating and stirring and obtains 3- methyl miaows
Azoles chloride salt ions liquid.The 3- methylimidazole villaumites ionic liquid and ferric chloride reaction that then will be obtained after hydrolysis, obtain iron
Base imidazole ion liquid.Then the MWNT of carboxylated adds DMF, DCC and DMAP, 1 0min of ultrasound with iron-based imidazole ion liquid
In 60.Heating stirring 24h under C.After completion of the reaction, after being centrifugally separating to obtain crude product, product is repeatedly washed with acetonitrile
And it is centrifuged off the impurity such as redundance.60 in last vacuum drying oven.C be dried to obtain CNT base 3- methyl iron-based imidazoles from
Sub- liquid B.
By 100 parts of epoxy resin composition (E-51:Epoxy A:TDE-85=100：30:10) with CNT base iron-based miaow
10 parts, the 20 parts polyethers amine epoxy curing agent D-230 mixing of oxazolinium ion liquid, stir, remove bubble, adhesive is made, puts
Put and obtain epoxide resin material after solidifying 24h at 20~25 DEG C and carry out performance test.
Testing standard：GB14569.2-1993《Low, middle level radioactive waste firming body performance requirement plastics solidification body》
Test result：Irradiation dose 106After Gy：
Compression strength：20MPa (reduce degree be less than 10%), 10m high perpendiculars drop to mattess do not produce it is bright
Aobvious fragmentation；
Freezing and thawing resistance：After freeze-thaw experiment, Volume Changes are less than 1%, are visible by naked eyes crack, and compression strength, which reduces, to be less than
10%；
Volumetric expansion is less than 2%；
Simulate water-resistance and anti-immersion：Sample leaches in 25 DEG C of deionized waters, the limitation of 42d correlations nuclide leaching rate
For Cs+＜ 5 × 10-4cm/d、Co2+＜ 1 × 10-4cm/d。
Embodiment 2
A certain amount of dichloroethanes, boron trifluoride ether solution and ethylene glycol are added in a kettle, after stirring,
Start that epoxychloropropane is added dropwise, whole reaction temperature control is at 18-23 DEG C.After epoxychloropropane is added dropwise, by reaction solution
40 DEG C are warming up to, reacts two hours.After question response liquid is cooled to room temperature, with saturated sodium bicarbonate solution and deionized water by its
Rinse repeatedly to neutrality, then be Based On Hydroxy-terminated Polyepichlorohydrin (PECH) after dichloroethanes is steamed.Homemade PECH is molten
In appropriate toluene, a certain amount of pure NaOH of analysis is added after being warming up to 90 DEG C, after reacting four hours, it is molten to add HCl/water
Liquid neutralizes remaining NaOH, is washed repeatedly with deionized water until solution is in neutrality, then is epoxy A after toluene is steamed, ring
Oxygen value is 0.14；
The chloromethanes newly distilled is added dropwise into 1- methylimidazoles, is reacted under 60 DEG C of condition of heating and stirring and obtains 3- butyl miaows
Azoles chloride salt ions liquid.The 3- butyl imidazole chloride salt ions liquid and ferric chloride reaction that then will be obtained after hydrolysis, obtain iron
Base imidazole ion liquid.Then the MWNT of carboxylated adds DMF, DCC and DMAP, 1 0min of ultrasound with iron-based imidazole ion liquid
In 60.Heating stirring 24h under C.After completion of the reaction, after being centrifugally separating to obtain crude product, product is repeatedly washed with acetonitrile
And it is centrifuged off the impurity such as redundance.60 in last vacuum drying oven.C be dried to obtain CNT base 3- butyl iron-based imidazoles from
Sub- liquid B.
By 100 parts of epoxy resin composition (E-51:A:TDE-85=100：40:10) with CNT base iron-based imidazoles from
Sub- 15 parts, 20 parts polyethers amine epoxy curing agent T-403 mixing of liquid, stir, remove bubble, adhesive is made, is placed on
Epoxide resin material is obtained after solidifying 24h at 20~25 DEG C and carries out performance test.
Testing standard：GB14569.2-1993《Low, middle level radioactive waste firming body performance requirement plastics solidification body》
Test result：After irradiation dose 106Gy：
Compression strength：20MPa (reduce degree be less than 10%), 10m high perpendiculars drop to mattess do not produce it is bright
Aobvious fragmentation；
Freezing and thawing resistance：After freeze-thaw experiment, Volume Changes are less than 1%, are visible by naked eyes crack, and compression strength, which reduces, to be less than
10%；
Volumetric expansion is less than 2%；
Simulate water-resistance and anti-immersion：Sample leaches in 25 DEG C of deionized waters, the limitation of 42d correlations nuclide leaching rate
For Cs+＜ 5 × 10-4cm/d、Co2+＜ 1 × 10-4cm/d。
Embodiment 3
A certain amount of dichloroethanes, boron trifluoride ether solution and ethylene glycol are added in a kettle, after stirring,
Start that epoxychloropropane is added dropwise, whole reaction temperature control is at 18-23 DEG C.After epoxychloropropane is added dropwise, by reaction solution
40 DEG C are warming up to, reacts two hours.After question response liquid is cooled to room temperature, with saturated sodium bicarbonate solution and deionized water by its
Rinse repeatedly to neutrality, then be Based On Hydroxy-terminated Polyepichlorohydrin (PECH) after dichloroethanes is steamed.Homemade PECH is molten
In appropriate toluene, a certain amount of pure NaOH of analysis is added after being warming up to 90 DEG C, after reacting four hours, it is molten to add HCl/water
Liquid neutralizes remaining NaOH, is washed repeatedly with deionized water until solution is in neutrality, then is epoxy A after toluene is steamed, ring
Oxygen value is 0.14；
The chloromethanes newly distilled is added dropwise into 1- methylimidazoles, is reacted under 60 DEG C of condition of heating and stirring and obtains 3- hexyl miaows
Azoles chloride salt ions liquid.The 3- hexyl imidazolium chloride salt ions liquid and ferric chloride reaction that then will be obtained after hydrolysis, obtain iron
Base imidazole ion liquid.Then the MWNT of carboxylated adds DMF, DCC and DMAP, 1 0min of ultrasound with iron-based imidazole ion liquid
In 60.Heating stirring 24h under C.After completion of the reaction, after being centrifugally separating to obtain crude product, product is repeatedly washed with acetonitrile
And it is centrifuged off the impurity such as redundance.60 in last vacuum drying oven.C be dried to obtain CNT base 3- hexyl iron-based imidazoles from
Sub- liquid B.
By 100 parts of epoxy resin composition (E-51:A:TDE-85=100：25:10) with CNT base iron-based imidazoles from
Sub- 15 parts, 10 parts polyethers amine epoxy curing agent T-5000 mixing of liquid, stir, remove bubble, adhesive is made, is placed on
Epoxide resin material is obtained after solidifying 24h at 20~25 DEG C and carries out performance test.
Testing standard：GB14569.2-1993《Low, middle level radioactive waste firming body performance requirement plastics solidification body》
Test result：Irradiation dose 106After Gy：
Compression strength：20MPa (reduce degree be less than 10%), 10m high perpendiculars drop to mattess do not produce it is bright
Aobvious fragmentation；
Freezing and thawing resistance：After freeze-thaw experiment, Volume Changes are less than 1%, are visible by naked eyes crack, and compression strength, which reduces, to be less than
10%%；
Volumetric expansion is less than 2%；
Simulate water-resistance and anti-immersion：Sample leaches in 25 DEG C of deionized waters, the limitation of 42d correlations nuclide leaching rate
For Cs+＜ 5 × 10-4cm/d、Co2+＜ 1 × 10-4cm/d
Embodiment 4
Epoxy A and CNT base iron-based imidazole ion liquid are prepared into using embodiment 1.
By 100 parts of epoxy resin composition (E-51:Epoxy A:TDE-85=100：40:10) with CNT base iron-based miaow
15 parts, the 15 parts polyethers amine epoxy curing agent T-5000 mixing of oxazolinium ion liquid, stir, remove bubble, adhesive is made, puts
Put and obtain epoxide resin material after solidifying 24h at 20~25 DEG C and carry out performance test.
Testing standard：GB14569.2-1993《Low, middle level radioactive waste firming body performance requirement plastics solidification body》
Test result：Irradiation dose 106After Gy：
Compression strength：20MPa (reduce degree be less than 10%), 10m high perpendiculars drop to mattess do not produce it is bright
Aobvious fragmentation；
Freezing and thawing resistance：After freeze-thaw experiment, Volume Changes are less than 1%, are visible by naked eyes crack, and compression strength, which reduces, to be less than
10%；
Volumetric expansion is less than 2%；
Simulate water-resistance and anti-immersion：Sample leaches in 25 DEG C of deionized waters, the limitation of 42d correlations nuclide leaching rate
For Cs+＜ 5 × 10-4cm/d、Co2+＜ 1 × 10-4cm/d。
As seen from the above embodiment, the invention provides a kind of epoxide resin material, by including following parts by weight of component
Raw material is made：100 parts of epoxy resin composition；10~20 parts of CNT base iron-based imidazole ion liquid；Amine terminated polyether 10
~20 parts；The epoxy resin composition includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepanes -1,2-
Dicarboxylic acid diglycidyl ester；The endurable active toughener has structure shown in formula I；The CNT base iron-based imidazole ion liquid tool
There is the structure of formula II.Epoxide resin material provided by the invention makes it have after irradiation well under the compatibility of said components
Mechanical performance and anti-leaching performance.Test result indicates that：Irradiation dose 106Afterwards, compression strength is that (reduction degree is less than 20MPa
10%), 10m high perpendiculars drop to mattess and do not produce obvious fragmentation；After freeze-thaw experiment, Volume Changes are less than 1%,
Crack is visible by naked eyes, compression strength, which reduces, is less than 10%；Volumetric expansion is less than 2%；Sample leaches in 25 DEG C of deionized waters,
Related nuclide leaching rate is limited to Cs within 42nd day+＜ 5 × 10-4cm/d、Co2+＜ 1 × 10-4cm/d。
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of epoxide resin material, it is made by the raw material including following parts by weight of component：
100 parts of epoxy resin composition；
10~20 parts of CNT base iron-based imidazole ion liquid；
10~20 parts of amine terminated polyether；
The epoxy resin composition includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- diformazans
Sour 2-glycidyl ester；The endurable active toughener has structure shown in formula I：
N=1~10；
The CNT base iron-based imidazole ion liquid has the structure of formula II：
The R is selected from-CH3,-C4H9,-C6H13Or-C11H23。
2. epoxide resin material according to claim 1, it is characterised in that the bisphenol A diglycidyl ether, activity increase
The mass ratio of tough dose and 4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters is 100:25~40:10~15.
3. epoxide resin material according to claim 1, it is characterised in that the amine terminated polyether is selected from model D-
230th, the one or more in D-200, T-403 and T-5000 amine terminated polyether.
4. epoxide resin material according to claim 1, it is characterised in that the endurable active toughener obtains epoxide number as 0.12
~0.14.
5. epoxide resin material according to claim 1, it is characterised in that the bisphenol A diglycidyl ether is selected from type
Number it is E-51 bisphenol A diglycidyl ethers；4,5- oxepanes -1,2- the dicarboxylic acid diglycidyl esters are selected from model
TDE-85 4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters.
6. epoxide resin material according to claim 1, it is characterised in that the endurable active toughener is by following methods system
：
A) after mixing dichloroethanes, boron trifluoride ether solution and ethylene glycol, epoxychloropropane is added dropwise, reaction, obtains
Reaction solution is rinsed to neutrality, then steams dichloroethanes, obtains Based On Hydroxy-terminated Polyepichlorohydrin；
B) toluene solution of Based On Hydroxy-terminated Polyepichlorohydrin and NaOH are reacted, obtained reaction solution is neutralized, washing, then by first
Benzene steams, and obtains endurable active toughener.
7. epoxide resin material according to claim 6, it is characterised in that in the step a) temperature of reaction for 38~
42℃；The time of reaction is 55~65min；
The temperature of reaction is 85~95 DEG C in the step b)；The time of reaction is 3.5~4.5h.
8. epoxide resin material according to claim 1, it is characterised in that the CNT base iron-based imidazol ion liquid
Body is made by following methods：
A) 1- alkyl imidazoles and chloromethanes are reacted, obtains 1- alkyl -3- methylimidazole villaumite ionic liquids；The 1- alkyl miaow
Alkyl is selected from methyl, butyl, hexyl or undecyl in azoles；By 1- alkyl -3- methylimidazole villaumites ionic liquid and tri-chlorination
Iron reacts, and obtains iron-based imidazole ion liquid；
B) in the presence of dimethylformamide, dicyclohexylcarbodiimide and DMAP, by carboxyl CNT
Reacted with iron-based imidazole ion liquid, obtain CNT base iron-based imidazole ion liquid.
9. epoxide resin material according to claim 8, it is characterised in that the carboxyl CNT and iron-based imidazoles from
The temperature of sub- liquid reactions is 55~65 DEG C；The time of carboxyl CNT and the reaction of iron-based imidazole ion liquid is 22~26h.
10. the preparation method of epoxide resin material, comprises the following steps described in a kind of claim 1~9 any one：
By 100 parts of epoxy resin composition, 10~20 parts of CNT base iron-based imidazole ion liquid and amine terminated polyether 10~
20 parts of mixing, solidification, obtain epoxide resin material.
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| CN116813917A (en) * | 2022-10-31 | 2023-09-29 | 张燕 | Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent |
| CN117567725A (en) * | 2024-01-15 | 2024-02-20 | 长春中科赫帝森材料科技有限公司 | Poly (epichlorohydrin) epoxy resin, preparation method thereof and epoxy resin cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109776979A (en) * | 2019-01-21 | 2019-05-21 | 华碳研发(深圳)有限公司 | Carbon nano tube-doped Ionic Liquid Modified butyl rubber resilient body and preparation method |
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| CN116813917A (en) * | 2022-10-31 | 2023-09-29 | 张燕 | Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent |
| CN117567725A (en) * | 2024-01-15 | 2024-02-20 | 长春中科赫帝森材料科技有限公司 | Poly (epichlorohydrin) epoxy resin, preparation method thereof and epoxy resin cured product |
| CN117567725B (en) * | 2024-01-15 | 2024-04-09 | 长春中科赫帝森材料科技有限公司 | Poly (epichlorohydrin) epoxy resin, preparation method thereof and epoxy resin cured product |
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