CN105367430A - Amine derivative containing adamantane structure and preparation method and application thereof - Google Patents
Amine derivative containing adamantane structure and preparation method and application thereof Download PDFInfo
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- CN105367430A CN105367430A CN201510627548.3A CN201510627548A CN105367430A CN 105367430 A CN105367430 A CN 105367430A CN 201510627548 A CN201510627548 A CN 201510627548A CN 105367430 A CN105367430 A CN 105367430A
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- bisphenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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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
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an amine derivative containing an adamantane structure and a preparation method and application thereof. The amine derivative solves the technical problem that in the prior art, a small quantity of adamantane and adamantane derivatives are applied to high polymers. The invention further discloses a molecular formula, the preparation method and application of the amine derivative. The amine derivative can meet the application requirement for electronic and composite materials and can be widely applied to aerospace, defense industry and other fields.
Description
Technical field
The invention belongs to the preparing technical field of modifier, solidifying agent, especially relate to the amino derivative and its preparation method and application containing adamantane structure.
Background technology
Diamantane (Adamantane) chemical name is three rings [3,3,1,13,7] decane is the ring-type tetrahedral carbon hydrogen compound be made up of 1O carbon atom and 16 hydrogen atoms, outward appearance is clear crystal, fusing point 268 DEG C, relative density 1.O7, refractive index 1.568, nontoxic, tasteless, easy distillation, water insoluble, be slightly soluble in benzene.The unit composition of diamantane is chair form conformation hexanaphthene, and whole ring system has symmetry and rigidity characteristic.Diamantane a kind ofly possesses the ester ring type carbohydrate that the carbonatoms constructing same structure with diamond is 1O, structure unit due to it is all the hexanaphthene of chair-type shape, therefore it to have structure neat, the feature that the transparency and stability etc. are excellent, under normal circumstances not with nitric acid and potassium permanganate effect, but easily there is SN1 type nucleophilic substitution reaction and SE2 type electrophilic substitution reaction in the hydrogen atom in its molecule.In addition, under certain condition, also the reaction of the types such as cytoskeleton rearrangement, oxidation, alkylation can be there is in diamantane molecule, its tool in medicine, functional polymer, lubricant, tensio-active agent, catalyzer, photographic material etc. is had been widely used, is described as fine chemical material of new generation.
Because diamantane has the characteristic of above excellence, it is made to show wide application prospect at functional materials neighborhood, as adamantane framework introduced main chain or the side chain of the polymkeric substance such as polyester, urethane, polymeric amide, polyimide, polyethers, polysulfones, polyethylene, the light transmission of polymkeric substance, wet-hot aging performance, dielectric properties, weather resistance, light fastness, thermostability performance, antioxidant property, chemical-resistant resistance and organic solvent corrosive nature etc. obviously can be improved.
In the past few decades, adamantane chemistry research has had significant progress, the process based prediction model of its many uniquenesses makes it can be applied in a lot of field, be mainly reflected in the production being applied to field of medicaments, being applied to senior lubricant and agrochemicals, adamantane derivative is penetrating in our daily life unconsciously.But the applied research in superpolymer of diamantane and derivative thereof is also less, and the technology such as activity enriched method that adamantane derivative applies in superpolymer and improve adamantane derivative also needs to deepen further along with research.
Summary of the invention
The present invention is exactly to solve diamantane that prior art exists and derivative applies less technical problem in superpolymer, provides a kind of amino derivative containing adamantane structure and its preparation method and application.
For this reason, the invention provides a kind of amino derivative containing adamantane structure, its chemical formula is represented by logical formula I:
In formula, R
1, R
2represent CH
2, CH
2cH
2, CH
2cH
2cH
2, CHCH
3, CHCH
3cH
2, CH
2cHCH
3, C (CH
3)
2, C (CH
3)
2cH
2, CH
2c (CH
3)
2cH
2; R
3, R
4represent H, OH, CH
3, Cl, Br, CF
3, R
1and R
2, R
3and R
4can be same structure, also can be different structure.
Preferably, R
1and R
2, R
3and R
4for same structure.
The present invention provides a kind of preparation method of the amino derivative containing adamantane structure simultaneously, and it is by diamantane phenol derivatives and react nitro halogen benzyl, then obtains through nitroreduction.
Preferably, containing the preparation method of the amino derivative of adamantane structure, it is characterized in that comprising the steps:
Step I: add magnetic rotor in flask, phenol 100 mass parts and 1.2 mass parts aluminum trichloride (anhydrous)s, by condensation reflux unit and device for absorbing tail gas stable connection, passing into nitrogen prevents phenol to be oxidized in reaction process, then oil bath temperature is raised, after the pre-hot melt of phenol, by 15 part 1, 3-dibromodiamantane adds uniform stirring in flask, then oil bath heats up, by 15 mass parts 1 after reaction, 3-dibromodiamantane adds flask, isothermal reaction is continued again after adding, finally be poured into agitator treating in hot water, after suction filtration, filter residue is repeated to drill and do until the color of filtrate after filtering is transparent, filter residue is through oven drying, obtain lightpink powder, the powder of above-mentioned lightpink is joined in flask, adds after dehydrated alcohol makes the saturated dissolving of product, heat up, add dilution heat of sulfuric acid, continue reflux, reaction terminates the cooling of rear room temperature, after the product suction filtration that crystallization goes out, uses deionized water repetitive scrubbing, recrystallization is carried out with dehydrated alcohol and deionized water mixed solution after dry,
Step II: add the first step product 20 mass parts in flask, p-nitrobenzyl chloride 25 mass parts, salt of wormwood 25 mass parts and acetonitrile, temperature rising reflux stirs; Suction filtration while hot after reaction terminates, filter residue absolute ethyl alcohol and stirring is washed, and dilute hydrochloric acid agitator treating twice, namely obtains target product after drying;
Step III: by second step product 20 mass parts, 0.5 mass parts Pd/C, wherein the mass percentage content of Pd is 10%, and tetrahydrofuran (THF) and dehydrated alcohol load flask; Heat up after passing into nitrogen, quality hundred parts of specific concentration 85% hydrazine hydrates load constant pressure funnel and slowly drip, and close after question response is stable in return line upper end with ball sealer, keep reaction pressure to stir; Reaction terminates rear filtered while hot Pd/C, and filtrate revolving is poured into after evaporating most of solvent in deionized water and separated out precipitation, and decompress filter obtains particulate state white solid, obtains target product finally after drying.
Invention provides a kind of amino derivative containing adamantane structure as promotor, resin to be carried out to the application of modification simultaneously.
Preferably, resin is bisphenol A cyanate ester resin, bisphenol E-type cyanate resin, bisphenol-f type cyanate ester resin, bisphenol S type cyanate ester resin, bis-phenol M type cyanate ester resin.
The present invention provides a kind of application be cured resin as solidifying agent containing the amino derivative of adamantane structure simultaneously.
Preferably, epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin, tetramethyl-bisphenol A type epoxy resin, linear phenolic epoxy resin, multiple functional radical glycidyl ether resin, multiple functional radical epihydric alcohol amine resin.
Effect of the present invention is: 1) simple synthetic method, low in raw material price, and productive rate is high and purity can reach more than 95%.Waste liquid can recycle and reuse; 2) by regulating the proportioning between cyanate matrix resin, additive, the New cyanide acid ester resin system that a kind of temperature of reaction reduces, high thermal resistance is good, comprehensive mechanical property is excellent, working life is long is provided; 3) excellent performances such as rear resin wet and heat ageing resistant, dielectric properties, dielectric properties are solidified.
Because in such amantadine analog derivative structure, aniline contains reactive hydrogen, so modification should can be carried out as the promotor of part resin containing the amino derivative of adamantane structure, also can use as ordinary resin solidifying agent, the synthesis of other polymkeric substance can be participated in simultaneously as monomer.The amantadine analog derivative of the present invention's synthesis has the advantages such as synthesis cycle is short, productive rate is high, waste liquid recycling capable of circulation, can suitability for industrialized production.The resin matrix of the amino derivative modification or solidification that simultaneously use this to contain adamantane structure significantly can reduce solidification value, and there is excellent wet-hot aging performance, dielectric properties, resistance to chemical corrosion and ageing-resistant performance, the application requiring of electronics, matrix material can be met completely, and the field such as aerospace, defence and military can be widely used in.
Below in conjunction with accompanying drawing, the present invention is further detailed.
Accompanying drawing explanation
Fig. 1 is adamantane derivative synthetic route chart of the present invention;
Fig. 2 is the infrared figure of adamantane derivative of the present invention;
Fig. 3 is final product nucleus magnetic hydrogen spectrum figure of the present invention;
Fig. 4 is final product nuclear-magnetism carbon spectrogram of the present invention;
Fig. 5 is final product mass spectrum of the present invention.
Embodiment
By following examples, embodiment of the present invention are described in detail.But the invention is not restricted to following examples.In each embodiment, 1,3-dibromodiamantane is produced by Wuhan Jin Nuo Chemical Co., Ltd.; Phenol, aluminum trichloride (anhydrous), acetonitrile, salt of wormwood, tetrahydrofuran (THF), 85% hydrazine hydrate is produced by Beijing Chemical Plant; Aluminum trichloride (anhydrous), Pd/C (Pd10%) and p-nitrobenzyl chloride are provided by Aladdin.
Embodiment 1
Step I:
Sizeable magnetic rotor is added in three mouthfuls of round-bottomed flasks of clean 250ml, 100g phenol and 1.2g aluminum trichloride (anhydrous), by condensation reflux unit and device for absorbing tail gas (water or dilute solution of sodium hydroxide) stable connection, passing into 1h nitrogen prevents phenol to be oxidized in reaction process, then raises oil bath temperature to 60 DEG C, after the pre-hot melt of phenol, by 15g1,3-dibromodiamantane adds uniform stirring in flask, and then oil bath is warmed up to 80 DEG C, reaction 2h.By 15g1,3-dibromodiamantane is divided 2 to 3 times and is added flask, each is spaced apart 2.5h or 1.5h, isothermal reaction 6h is continued again after adding, finally be poured into agitator treating in the hot water of 65 DEG C, repeated by filter residue after suction filtration to drill and do until the color of filtrate after filtering is transparent, filter residue, through oven drying, obtains lightpink powder.The powder of above-mentioned lightpink is joined in three mouthfuls of round-bottomed flasks, add appropriate dehydrated alcohol and make product after 60 DEG C of saturated dissolvings, be warming up to 90 DEG C.Add the dilution heat of sulfuric acid of appropriate 1mol/L, continue reflux 2h.Reaction terminates the cooling of rear room temperature, after the product suction filtration that crystallization goes out, uses deionized water repetitive scrubbing.Recrystallization is carried out with dehydrated alcohol and deionized water mixed solution after dry.
Step II:
In 250ml single port flask, add the first step product (20g, 0.0625mol), p-nitrobenzyl chloride (25g, 0.146mol), salt of wormwood (25g, 0.181mol) and 200ml acetonitrile, be warmed up to 85 DEG C of return stirring 5h.Suction filtration while hot after reaction terminates, filter residue absolute ethyl alcohol and stirring washes twice, and 1mol/L dilute hydrochloric acid agitator treating twice, namely obtains target product after drying.
Step III:
By 20g second step product, 0.5gPd/C (Pd5%), 300ml tetrahydrofuran (THF) loads 1000ml tri-mouthfuls of round-bottomed flasks with 150ml dehydrated alcohol and is connected constant pressure funnel and condensing reflux pipe.After passing into 1 hour nitrogen, temperature is raised to 95 DEG C, and 100ml hydrazine hydrate (85%) loads constant pressure funnel and slowly drips, and closes after question response is stable in return line upper end with ball sealer, keeps reaction pressure to stir 8h.Reaction terminates rear filtered while hot Pd/C, and filtrate revolving is poured into after evaporating most of solvent in deionized water and separated out precipitation, and decompress filter obtains particulate state white solid, obtains target product finally after drying.
Embodiment 2
Step I is identical with embodiment 1.
Step II:
In 250ml single port flask, add the first step product (20g, 0.0625mol), p-nitrobenzyl chloride (25g, 0.146mol), salt of wormwood (25g, 0.181mol) and 200ml acetonitrile, be warmed up to 75 DEG C of return stirring 8h.Suction filtration while hot after reaction terminates, filter residue absolute ethyl alcohol and stirring washes twice, and 1mol/L dilute hydrochloric acid agitator treating twice, namely obtains target product after drying.
Step III:
By 20g second step product, 0.5gPd/C (Pd10%), 300ml tetrahydrofuran (THF) loads 1000ml tri-mouthfuls of round-bottomed flasks with 150ml dehydrated alcohol and is connected constant pressure funnel and condensing reflux pipe.After passing into 1 hour nitrogen, temperature is raised to 95 DEG C, and 100ml hydrazine hydrate (85%) loads constant pressure funnel and slowly drips, and closes after question response is stable in return line upper end with ball sealer, keeps reaction pressure to stir 6h.Reaction terminates rear filtered while hot Pd/C, and filtrate revolving is poured into after evaporating most of solvent in deionized water and separated out precipitation, and decompress filter obtains particulate state white solid, obtains target product finally after drying.
Embodiment 3
Step I, II identical with embodiment 1.
Step III is identical with embodiment 2.
Embodiment 4
Step I, II, III identical with embodiment 3.
Bisphenol A cyanate ester resin is melted at 100 DEG C, fully stirs after adding the target product of 2%.After mixing, pour mould into by heating schedule 120 DEG C/2h, 160 DEG C/2h, 200 DEG C/3h, 240 DEG C/2h makes test bars.
Embodiment 5
Step I, II, III identical with embodiment 3.
Bisphenol A cyanate ester resin is melted at 100 DEG C, fully stirs after adding the target product of 5%.After mixing, pour mould into by heating schedule 120 DEG C/2h, 160 DEG C/2h, 200 DEG C/3h, 240 DEG C/2h makes test bars.
Embodiment 6
Step I, II, III identical with embodiment 3.
TGE-85 epoxy fat resin is stirred at 100 DEG C, fully stirs after adding the target product after calculating according to epoxy equivalent (weight).After mixing, pour mould into by heating schedule 120 DEG C/2h, 140 DEG C/2h, 160 DEG C/3h, 180 DEG C/2h makes test bars.
Claims (8)
1., containing an amino derivative for adamantane structure, it is characterized in that its chemical formula is as shown in logical formula I:
In formula, R
1, R
2represent CH
2, CH
2cH
2, CH
2cH
2cH
2, CHCH
3, CHCH
3cH
2, CH
2cHCH
3, C (CH
3)
2, C (CH
3)
2cH
2, CH
2c (CH
3)
2cH
2; R
3, R
4represent H, OH, CH
3, Cl, Br, CF
3, R
1and R
2, R
3and R
4can be same structure, also can be different structure.
2. the amino derivative containing adamantane structure according to claim 1, is characterized in that R
1and R
2, R
3and R
4for same structure.
3. the preparation method of the amino derivative containing adamantane structure as claimed in claim 1, is characterized in that by diamantane phenol derivatives and reacts nitro halogen benzyl, then obtaining through nitroreduction.
4. the preparation method of the amino derivative containing adamantane structure according to claim 3, is characterized in that comprising the steps:
Step I: add magnetic rotor in flask, phenol 100 mass parts and 1.2 mass parts aluminum trichloride (anhydrous)s, by condensation reflux unit and device for absorbing tail gas stable connection, passing into nitrogen prevents phenol to be oxidized in reaction process, then oil bath temperature is raised, after the pre-hot melt of phenol, by 15 part 1, 3-dibromodiamantane adds uniform stirring in flask, then oil bath heats up, by 15 mass parts 1 after reaction, 3-dibromodiamantane adds flask, isothermal reaction is continued again after adding, finally be poured into agitator treating in hot water, after suction filtration, filter residue is repeated to drill and do until the color of filtrate after filtering is transparent, filter residue is through oven drying, obtain lightpink powder, the powder of above-mentioned lightpink is joined in flask, adds after dehydrated alcohol makes the saturated dissolving of product, heat up, add dilution heat of sulfuric acid, continue reflux, reaction terminates the cooling of rear room temperature, after the product suction filtration that crystallization goes out, uses deionized water repetitive scrubbing, recrystallization is carried out with dehydrated alcohol and deionized water mixed solution after dry,
Step II: add the first step product 20 mass parts in flask, p-nitrobenzyl chloride 25 mass parts, salt of wormwood 25 mass parts and acetonitrile, temperature rising reflux stirs; Suction filtration while hot after reaction terminates, filter residue absolute ethyl alcohol and stirring is washed, and dilute hydrochloric acid agitator treating twice, namely obtains target product after drying;
Step III: by second step product 20 mass parts, 0.5 mass parts Pd/C, wherein the mass percentage content of Pd is 10%, and tetrahydrofuran (THF) and dehydrated alcohol load flask; Heat up after passing into nitrogen, quality hundred parts of specific concentration 85% hydrazine hydrates load constant pressure funnel and slowly drip, and close after question response is stable in return line upper end with ball sealer, keep reaction pressure to stir; Reaction terminates rear filtered while hot Pd/C, and filtrate revolving is poured into after evaporating most of solvent in deionized water and separated out precipitation, and decompress filter obtains particulate state white solid, obtains target product finally after drying.
5. the amino derivative containing adamantane structure as claimed in claim 1 carries out the application of modification to resin as promotor.
6. the amino derivative containing adamantane structure according to claim 5 carries out the application of modification to resin as promotor, it is characterized in that described resin is bisphenol A cyanate ester resin, bisphenol E-type cyanate resin, bisphenol-f type cyanate ester resin, bisphenol S type cyanate ester resin, bis-phenol M type cyanate ester resin.
7. the application as solidifying agent, resin is cured containing the amino derivative of adamantane structure as claimed in claim 1.
8. the application be cured resin as solidifying agent containing the amino derivative of adamantane structure according to claim 7, is characterized in that described epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin, tetramethyl-bisphenol A type epoxy resin, linear phenolic epoxy resin, multiple functional radical glycidyl ether resin, multiple functional radical epihydric alcohol amine resin.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106589455A (en) * | 2016-12-16 | 2017-04-26 | 广东工业大学 | Sulfonate type flame retardant and preparation method thereof and polycarbonate composite material and preparation method thereof |
| CN106589454A (en) * | 2016-12-16 | 2017-04-26 | 广东工业大学 | Fire retardant, preparation method thereof, composite polycarbonate material, and preparation method thereof |
| CN110330688A (en) * | 2019-06-03 | 2019-10-15 | 盐城市朗创新材料有限公司 | Dedicated stabilizer of charging pile cable and preparation method thereof |
| CN110590710A (en) * | 2019-09-17 | 2019-12-20 | 西北工业大学 | Bisphenol AF type epoxy end group adamantane and preparation method thereof, and high-wave-transmittance resin matrix and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589455A (en) * | 2016-12-16 | 2017-04-26 | 广东工业大学 | Sulfonate type flame retardant and preparation method thereof and polycarbonate composite material and preparation method thereof |
| CN106589454A (en) * | 2016-12-16 | 2017-04-26 | 广东工业大学 | Fire retardant, preparation method thereof, composite polycarbonate material, and preparation method thereof |
| CN110330688A (en) * | 2019-06-03 | 2019-10-15 | 盐城市朗创新材料有限公司 | Dedicated stabilizer of charging pile cable and preparation method thereof |
| CN110330688B (en) * | 2019-06-03 | 2021-10-29 | 盐城市朗创新材料有限公司 | Special environment-friendly stabilizer for charging pile cable and preparation method thereof |
| CN110590710A (en) * | 2019-09-17 | 2019-12-20 | 西北工业大学 | Bisphenol AF type epoxy end group adamantane and preparation method thereof, and high-wave-transmittance resin matrix and preparation method thereof |
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