CN110423223A - A kind of preparation method and its epoxidation application of Phthalazinone biphenol monomer - Google Patents
A kind of preparation method and its epoxidation application of Phthalazinone biphenol monomer Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006735 epoxidation reaction Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000006887 Ullmann reaction Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- VIOFYLQVVYLKOM-UHFFFAOYSA-N C(C)[N+](CC1=CC=CC=C1)(CC)CC.[Cl+] Chemical compound C(C)[N+](CC1=CC=CC=C1)(CC)CC.[Cl+] VIOFYLQVVYLKOM-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 230000000979 retarding effect Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- -1 Bisphenol compound Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229920000090 poly(aryl ether) Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000005054 naphthyridines Chemical class 0.000 description 2
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/30—Phthalazines
- C07D237/32—Phthalazines with oxygen atoms directly attached to carbon atoms of the nitrogen-containing ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- 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
- C08G59/26—Di-epoxy compounds heterocyclic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to new material technology fields, disclose the preparation method and its epoxidation application of a kind of Phthalazinone biphenol monomer.Steps are as follows: (1) Friedel-Crafts reaction prepares MHPZ；(2) with MHPZ, BPM, PNTM and CuI, MMPZ monomer has been synthesized using " one pot of two-step method "；(3) MMPZ is restored to obtain subject monomers HHPZ through lewis acid.Synthetic reaction condition of the invention has reaction condition mild, the advantage that product postprocessing is easy and product purity is high.Purity through LC-MS test target monomer is 99%, 90% or more yield.It is explored based on above-mentioned synthesis, by the further functionalization in both ends of the active biphenol monomer of synthesis.The activity hydroxy at the both ends HHPZ carries out epoxidation with epoxychloropropane, has obtained low melting point, novel intrinsic fire retarding epoxide resin resistant to high temperature, flame retardant rating is up to V-0 grades.
Description
Technical field
The invention belongs to new material technology field, a kind of preparation method of Phthalazinone biphenol monomer (HHPZ).
Background technique
Bisphenol compound is the primary raw material for synthesizing polyarylate, polyarylether, epoxy resin and polysulfones resinoid, will be special
Different functional group introduces main polymer chain, and then improves service performance (temperature tolerance, anti-flammability, the optical property, thoroughly of polymer
Wave or absorbing property etc.).This patent preparation synthesis biphenol monomer in ehter bond can both increase main polymer chain ductility and
Flexibility, and the fusing point of polymer can be reduced；Meanwhile the special distortion non-co-planar structure of Phthalazinone can improve polymerization
Arrangement between object segment can assign polymer heat resistance outstanding and dissolubility.Such as the poly(aryl ether ketone) in traditional polyarylether
Class material, belongs to semi-crystalline polymer, has excellent chemical stability and mechanical performance, but dissolubility is poor, under room temperature
It is only soluble in the concentrated sulfuric acid.However, in polyarylether system introduce Phthalazinone after prepare a series of polymer (PPESK,
PPENK, PPES etc.) show excellent temperature tolerance and dissolubility.To have full aromatic ring, distortion, non-co-planar benzodiazine
The biphenol monomer function of ring structure turns to epoxy resin, balances the relationship between processability and service performance.
Summary of the invention
The purpose of the present invention is a kind of preparation method of Phthalazinone biphenol monomer and its epoxidation applications.
Technical solution of the present invention:
A kind of preparation method of Phthalazinone biphenol monomer, steps are as follows:
(1) Friedel-Crafts reaction prepares unilateral methoxy monomer (MHPZ)；
(2) with MHPZ, BPM (para-bromoanisole), PNTM (1,10- Phen) and CuI (cuprous iodide), using " one
Pot two-step method " has synthesized bilateral methoxy monomer (MMPZ)；
(3) MMPZ is restored to obtain double hydroxyl subject monomers (HHPZ) through lewis acid；
The synthetic route of MHPZ, MMPZ and HHPZ are as follows:
(1) Friedel-Crafts reaction prepares MHPZ the specific method is as follows: under ice bath environment, using methylene chloride as reaction dissolvent,
Alchlor (AlCl3) it is catalyst, reactant PA:AS:AlCl3Between molar ratio be 1:1.5:1.5, reactant feeds intake completion
Afterwards, continue to stir 1h under ice bath environment；Above-mentioned mixed system is reacted into 3h at 25 DEG C, sinks to ice acid bath after reaction
In, obtain white solid powder；The mixing that above-mentioned white solid powder is dissolved in sulfolane and chlorobenzene that volume ratio is 3:1 is molten
In liquid, 30min is mixed at 110 DEG C, corresponding reactant intermediate sour (product of PA and AS) mole point is then added dropwise
Several hydrazine hydrates maintains 2h at such a temperature, will finally filter after reaction solution cooling and obtains needle-like white solid, as MHPZ；
(2) the specific method is as follows by a kind of bi-methoxy MMPZ prepared containing naphthyridine ketone structure: stirring to equipped with machinery
It mixes, MHPZ and K is added in the three-necked flask of reflux condensate device2CO3, K2CO3Dosage be 2.5 times of MHPZ mole, In
Salt-forming reaction 5-6 hours at 140-150 DEG C, after salt-forming reaction, reaction solution is down to room temperature, it is even that Liv Ullmann is then added
Join ligand PNTM, catalyst CuI and reactant B PM, is protected from light 12-24h, reaction temperature is gradually heated to 160- by room temperature
It 180 DEG C, after reaction, will be sunk in hot water after reaction solution cooling, it is overnight to drain, brown solid is dissolved in chloroform, filters institute
It obtains filtrate and excessive anhydrous sodium sulfate water removal is added, obtain light yellow powder solid after revolving, ethyl alcohol is rinsed 1-2 times, obtained
White solid is placed in 10~12h of vacuum drying in 100 DEG C of vacuum ovens；Wherein, mole of MHPZ, BPM, PNTM and CuI
Than for 1:1.5-2:0.01-0.02:0.05-0.15；
(3) the specific method is as follows by a kind of biphenol monomer HHPZ containing naphthyridine ketone structure: to equipped with mechanical stirring and return
It flows and MMPZ, CH is added in the three-necked flask of condensing unit3CN and KI, solvent C H3CN dosage is every 5g MMPZ addition
100mLCH3CN, feed ratio MMPZ:KI:AlCl3AlCl is added at 0 DEG C in=1:12-16:12-16 in batches3In ice bath ring
AlCl is added under border in batches3, and after continuously stirring 1h, by reaction solution as being reacted for 24 hours at 60-90 DEG C；Reaction solution is cooling
After sink in ice sour water, be collected into pale yellow powder, white solid can be obtained with the mixed liquor repeated flushing of second alcohol and water.
A kind of bifunctionality epoxy containing Phthalazinone EEPZ's the preparation method is as follows: to magnetic agitation is equipped with
HHPZ, benzyltriethylammoinium chloride and epoxy is added according to molar ratio (1:0.15:50) in the there-necked flask of reflux condensate device
Chloropropane reacts 3h at 85 DEG C, is that the NaOH that 1:2.5 dropwise addition mass fraction is 40% is water-soluble by HHPZ:NaOH molar ratio
Liquid, and 1h is reacted at the same temperature, it repeatedly washes, and vacuum rotary steam removes extra water and epoxychloropropane, obtains transparent
Sticky mass.
Beneficial effects of the present invention: synthetic reaction condition of the invention has reaction condition mild, and product postprocessing is easy
And the advantage that product purity is high.Purity through LC-MS test target monomer is 99%, 90% or more yield.Based on above-mentioned
Synthesis is explored, by the further functionalization in both ends of the active biphenol monomer of synthesis.The same epoxy chloropropionate of the activity hydroxy at the both ends HHPZ
Alkane carries out epoxidation, has obtained low melting point, novel intrinsic fire retarding epoxide resin resistant to high temperature, flame retardant rating is up to V-0 grades.
Detailed description of the invention
Fig. 1 is MHPZ nuclear magnetic spectrogram.
Fig. 2 is MMPZ nuclear magnetic spectrogram.
Fig. 3 is HHPZ nuclear magnetic spectrogram.
Fig. 4 is EEPZ nuclear magnetic spectrogram.
Fig. 5 is the LC-MS spectrogram of HHPZ.
Fig. 6 is the alternating temperature rheological curve of EEPZ.
Fig. 7 is the constant temperature rheological curve of EEPZ.
Specific embodiment
Only the present invention is further illustrated for the case study on implementation being provided below, but does not limit the scope of the invention.
Case 1 is the preparation case of the monomer of mono methoxy containing Phthalazinone (MHPZ).
Case study on implementation 1
Using methylene chloride as reaction dissolvent, alchlor (AlCl3) is catalyst, and ice bath feeds intake, reactant (PA:AS:
AlCl3) between molar ratio be 1:1.5:1.5, after the completion of feeding intake, continue under ice bath environment stir 1h.By above-mentioned mixed system
3h is reacted at 25 DEG C, is sunk in ice acid bath after reaction, is obtained white solid powder.Above-mentioned white solid powder is molten
In the mixed solution of sulfolane and chlorobenzene (volume ratio 3:1), 30min is mixed at 110 DEG C, is then added dropwise and corresponds to
The hydrazine hydrate of reactant molar fraction maintains 2h at such a temperature, finally will reaction solution it is cooling after filter and obtain needle-like white and consolidate
Body.
As shown in Fig. 2 nuclear magnetic spectrogram, chemical shift 8.4ppm or so is the absorption peak of the peri-position hydrogen on diaza naphthalene nucleus,
It on the basis of H herein, can be accurately positioned in compound MHPZ, generate the chemical shift at the peak functional group N-H about in 12.7ppm
Near, while nearby also there is the characteristic peak of methoxyl group in chemical shift 3-4ppm.
Case 2 is the preparation case of the monomer of dimethoxy containing naphthyridine ketone structure (MMPZ).
Case study on implementation 2: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light for 24 hours, and reaction temperature is gradually heated to 160 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
Case study on implementation 3: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light 18h, and reaction temperature is gradually heated to 170 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
Case study on implementation 4: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light 12h, and reaction temperature is gradually heated to 180 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
Case study on implementation 5: MHPZ and K is added into the three-necked flask equipped with magnetic agitation, reflux condensate device2CO3, In
Salt-forming reaction 5-6 hours at 145 DEG C, after salt-forming reaction, reaction solution is down to room temperature, Liv Ullmann coupling is then added and matches
Body PNTM, catalyst CuI and reactant B PM, are protected from light 18h, and reaction temperature is gradually heated to 180 DEG C by room temperature.Reaction knot
Shu Hou will be sunk in hot water after reaction solution cooling, overnight to drain, and brown color solid is dissolved in chloroform, gained filtrate is filtered and is added
Excessive anhydrous sodium sulfate removes water, and light yellow powder solid is obtained after revolving, and ethyl alcohol rinses 1-2 times, obtains white solid, set
10~12h is dried in vacuo in 100 DEG C of vacuum ovens.
As shown in Fig. 3 nuclear magnetic spectrogram, by chemical shift 8.4ppm or so be diaza naphthalene nucleus on peri-position hydrogen on the basis of,
Its near 3-4ppm the ratio between peak area be 1:6, in addition, also occurring phenyl ring hydrogen characteristic peak at 6.7ppm, it was demonstrated that MHPZ
C-N coupling reaction success between BPM.
Case 3 is the preparation case of biphenol monomer containing naphthyridine ketone structure (HHPZ)
Case study on implementation 6: being added MMPZ into the three-necked flask equipped with mechanical stirring, reflux condensate device, and in molar ratio 1:
12 are added AlCl3, in 0 DEG C of CH3After continuously stirring 1h in CN and KI system, by reaction solution as being reacted for 24 hours at 90 DEG C.It will reaction
Liquid cooling is but sunk in ice sour water afterwards, is collected into pale yellow powder, and white can be obtained with the mixed liquor repeated flushing of second alcohol and water
Solid.
Case study on implementation 7: being added MMPZ into the three-necked flask equipped with magnetic agitation, reflux condensate device, and in molar ratio 1:
16 are added AlCl3, in 0 DEG C of CH3After continuously stirring 1h in CN and KI system, by reaction solution as being reacted for 24 hours at 90 DEG C.It will reaction
Liquid cooling is but sunk in ice sour water afterwards, is collected into pale yellow powder, and white can be obtained with the mixed liquor repeated flushing of second alcohol and water
Solid.
Case study on implementation 8: being added MMPZ into the three-necked flask equipped with magnetic agitation, reflux condensate device, and in molar ratio 1:
16 are added AlCl3, in 0 DEG C of CH3After continuously stirring 1h in CN and KI system, by reaction solution as being reacted for 24 hours at 90 DEG C.It will reaction
Liquid cooling is but sunk in ice sour water afterwards, is collected into pale yellow powder, and white can be obtained with the mixed liquor repeated flushing of second alcohol and water
Solid.
As shown in Fig. 4 nuclear magnetic spectrogram, occur phenolic hydroxyl group absorption peak between chemical shift 9.5-10ppm, meanwhile, 3-4 it
Between methoxyl group characteristic peak peak disappear, show that MMPZ is successfully reduced to HHPZ.And by LC-MS as shown in fig. 6, into one
Step characterizes product purity.
Case 4 is the preparation case of epoxy containing naphthyridine ketone structure (EEPZ)
Case study on implementation 9: into the there-necked flask equipped with magnetic agitation and reflux condensate device according to molar ratio (1:0.15:
50) HHPZ, benzyltriethylammoinium chloride and epoxychloropropane is added, reacts 3h at 85 DEG C, is by HHPZ:NaOH molar ratio
1:2.5 is added dropwise mass fraction and is 40% NaOH aqueous solution, and reacts 1h at the same temperature, repeatedly washes, and vacuum rotary steam
Extra water and epoxychloropropane are removed, transparent sticky mass is obtained.
As shown in figure 5, occurring the proton peak on epoxy alkyl chain at 2.5-4.5ppm, show the both ends HHPZ epoxy
Change is completed.Simultaneously rheometer test characterization has been carried out to the processing performance of EEPZ epoxy, by Fig. 6 it is found that EEPZ epoxy have compared with
Low fusing point is about 65 DEG C, and process window is about 85-225 DEG C wider.The gel time of EEPZ resin is about known to Fig. 7
45min.In addition, vertical burn test the results show that for the first time light flame, extinguish in 4s, after lighting for the second time
Extinguish in 10s, no molten drop is low, and flame retardant rating is up to V-0 grades.
Claims (2)
1. a kind of preparation method of Phthalazinone biphenol monomer, which is characterized in that steps are as follows:
The synthetic route of MHPZ, MMPZ and HHPZ are as follows:
(1) Friedel-Crafts reaction prepares MHPZ the specific method is as follows:
Under ice bath environment, using methylene chloride as reaction dissolvent, AlCl3For catalyst, reactant PA:AS:AlCl3Between mole
Than after the completion of reactant feeds intake, continuing to stir 1h under ice bath environment for 1:1.5:1.5；By above-mentioned mixed system at 25 DEG C
3h is reacted, is sunk in ice acid bath after reaction, obtains white solid powder；Above-mentioned white solid powder, which is dissolved in volume ratio, is
In the sulfolane of 3:1 and the mixed solution of chlorobenzene, 30min is mixed at 110 DEG C, corresponding reactant intermediate is then added dropwise
The hydrazine hydrate of sour molar fraction maintains 2h at such a temperature, will finally filter after reaction solution cooling and obtains needle-like white solid, i.e.,
For MHPZ；
(2) the specific method is as follows by a kind of bi-methoxy MMPZ prepared containing naphthyridine ketone structure:
MHPZ and K is added into the three-necked flask equipped with mechanical stirring, reflux condensate device2CO3, K2CO3Dosage be that MHPZ rubs
2.5 times of that amount, salt-forming reaction 5-6 hours at 140-150 DEG C, after salt-forming reaction, are down to room temperature for reaction solution, then
Liv Ullmann coupling ligand PNTM, catalyst CuI and reactant B PM is added, is protected from light 12-24h, reaction temperature by room temperature gradually
It is warming up to 160-180 DEG C, after reaction, will be sunk in hot water after reaction solution cooling, it is overnight to drain, brown solid is dissolved in chlorine
It is imitative, it filters gained filtrate and excessive anhydrous sodium sulfate water removal is added, obtain light yellow powder solid after revolving, ethyl alcohol rinses 1-2
Time, white solid is obtained, is placed in 100 DEG C of vacuum ovens and is dried in vacuo 10~12h to get MMPZ；Wherein, MHPZ, BPM,
The molar ratio of PNTM and CuI is 1:1.5-2:0.01-0.02:0.05-0.15；
(3) the specific method is as follows by a kind of biphenol monomer HHPZ containing naphthyridine ketone structure:
MMPZ, CH are added into the three-necked flask equipped with mechanical stirring and reflux condensate device3CN and KI is added in batches at 0 DEG C
AlCl3AlCl is added in batches under ice bath environment3, and after continuously stirring 1h, by reaction solution as being reacted for 24 hours at 60-90 DEG C；
Solvent C H3CN dosage is that 100mLCH is added in every 5g MMPZ3CN, feed ratio MMPZ:KI:AlCl3=1:12-16:12-16；It will
It is sunk in ice sour water after reaction solution is cooling, is collected into pale yellow powder, with the mixed liquor repeated flushing of second alcohol and water up to white
Solid is HHPZ.
2. a kind of preparation method of the bifunctionality epoxy EEPZ containing Phthalazinone, which is characterized in that steps are as follows: to
HHPZ, benzyl triethyl ammonium chlorine is added according to molar ratio 1:0.15:50 in there-necked flask equipped with magnetic agitation and reflux condensate device
Change ammonium and epoxychloropropane, react 3h at 85 DEG C, is that mass fraction is added dropwise is 40% to 1:2.5 by HHPZ:NaOH molar ratio
NaOH aqueous solution, and 1h is reacted at the same temperature, it repeatedly washes, and vacuum rotary steam removes extra water and epoxychloropropane,
Obtain transparent sticky mass.
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| CN111530298A (en) * | 2020-05-12 | 2020-08-14 | 福建师范大学 | Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group |
| CN111704581A (en) * | 2019-07-26 | 2020-09-25 | 大连理工大学 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
| CN118580771A (en) * | 2024-08-05 | 2024-09-03 | 广州赫厉狮森汽车用品有限公司 | Preparation method of light automobile chassis adhesive with good sound insulation effect |
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| CN102585225B (en) * | 2011-05-20 | 2014-10-22 | 大连理工大学 | Preparation method of diaza-naphthalenone-biphenyl-polybenzoxazole, monomer and polymer |
| CN106905136A (en) * | 2017-02-08 | 2017-06-30 | 泰力特医药（湖北）有限公司 | A kind of preparation method of 2 (4 (2-hydroxybenzoyl)) benzoic acid |
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| CN109851563B (en) * | 2019-03-04 | 2022-06-14 | 大连理工大学 | Preparation method of bisphenol monomer containing phthalazinone structure |
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| CN111704581A (en) * | 2019-07-26 | 2020-09-25 | 大连理工大学 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
| CN111704581B (en) * | 2019-07-26 | 2021-08-24 | 大连理工大学 | Heteronaphthalene biphenyl bisphenol monomer and preparation method thereof, heteronaphthalene biphenyl epoxy monomer and preparation method and application thereof, and flame-retardant epoxy resin |
| CN111530298A (en) * | 2020-05-12 | 2020-08-14 | 福建师范大学 | Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group |
| CN111530298B (en) * | 2020-05-12 | 2021-11-23 | 福建师范大学 | Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group |
| CN118580771A (en) * | 2024-08-05 | 2024-09-03 | 广州赫厉狮森汽车用品有限公司 | Preparation method of light automobile chassis adhesive with good sound insulation effect |
| CN118580771B (en) * | 2024-08-05 | 2024-10-01 | 广州赫厉狮森汽车用品有限公司 | Preparation method of light automobile chassis adhesive with good sound insulation effect |
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