CN1974546A - Diphenol derivative containing aromatic schiff base and ether band structure and its prepn and application - Google Patents
Diphenol derivative containing aromatic schiff base and ether band structure and its prepn and application Download PDFInfo
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- CN1974546A CN1974546A CN 200610155092 CN200610155092A CN1974546A CN 1974546 A CN1974546 A CN 1974546A CN 200610155092 CN200610155092 CN 200610155092 CN 200610155092 A CN200610155092 A CN 200610155092A CN 1974546 A CN1974546 A CN 1974546A
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Abstract
The present invention discloses one kind of diphenol derivative containing aromatic Schiff base and ether band structure of the general expression as shown. The diphenol derivative may be used in preparing nitrogenous epoxy resin, other diphenol derivative and nitrogenous epoxy resin composition. The nitrogenous epoxy resin is used in making high performance laminate.
Description
Technical field
The present invention relates to a class and contain the diphenol derivative of aromatic schiff base and diether linkage structure and the technology of application thereof.Be specifically related to have excellent over-all propertieies such as high heat-resisting, high glass-transition temperature, UV barrier functionality and flame retardant resistance, can be used as the epoxy resin component of insulating material in the electric field, and their manufacture method.
Background of invention:
Thermostability, insulativity, cohesiveness, good mechanical performance, good building-up properties reach lower advantages such as cost to epoxy resin cured product owing to have preferably, be widely used in bonding, the encapsulation of electronic devices and components and the manufacturing of printed circuit board (PCB), being one of present of paramount importance electron chemistry material, is the mainstay that supports electric industry.Yet the same with most of macromolecular materials, the curable epoxide thing is inflammable, and the fire that the annual whole world therefore causes has caused huge loss of life and personal injury and property damage, therefore necessary the curable epoxide thing that is applied in electric field is carried out fire-retardant finish.
In recent decades, widely used in electric field is to be monomeric brominated Resins, epoxy with tetrabromo-bisphenol, with bromine flame retardant epoxy cured article.Yet brominated Resins, epoxy discharges toxic substance in burning or waste treatment, as produces a large amount of dense smokes and irritating toxic gas.Therefore need to seek the environment friendly flame retardant that substitutes bromine.The Resins, epoxy that is used for electric field at present also suffers from another huge predicament.Because plumbous baneful influence to environment and human health, traditional slicker solder weldprocedure is eliminated gradually.European Union " electric and electronics offal treatment method (Waste Electrical and Electronic Equipment; WEEE) " and " in the electronic electric equipment restriction use some objectionable impurities instruction (Restriction of certain HazardousSubstances; RoHS) " draft for amendments, to Halogen, unleaded environmental protection electronic material standard in addition.Clearly regulation lead, mercury, cadmium, chromium (6 valency), Polybrominated biphenyl (PBB) and six kinds of chemical substances of polybromodiphenyl ether (PBDE) forbade using in electronic and electrical equipment from July 1st, 2006.This means and in various electronic products, must use leadless process that base material is processed, cause unpredictable harm in the product to avoid lead is incorporated into.Because the welding temperature of lead-free solder has the welding temperature of lead solder apparently higher than tradition, so require the thermosetting resin base material of carrying electric elements to have higher thermostability.Thereby this regulation (comprises second-order transition temperature T to the thermostability that the curable epoxide thing that is used for electronic substrate has proposed more harsh performance requriements, particularly material
g, initial heat decomposition temperature T
d, thermal linear expansion coefficient Z-CTE etc.) and processing characteristics.The manufacturing issue of the curable epoxide thing that fire-retardant a, high heat resistance and workability have both to sum up, has in fact been proposed.
The WEEE/RoHS of European Union instruction has begun to carry out, and the Resins, epoxy of consumption maximum needs to change as early as possible to satisfy these requirements in the electronic material.This comprises that " unleaded " that must carry out of regulation requires (needing to improve the thermal stability of material) in the RoHS instruction, comprise that also " non-halogen " that RoHS instruction suggestion is carried out requires (need satisfy the Environmental compatibility in material use and the degradation process, notice that tetrabromo-bisphenol is not among above-mentioned forbidden six kinds of materials, can continue to use about it, environmentalist and industrial community are also among debating actively, but electronic substrate " non-halogen " is the megatrend in this field).For tackling these requirements, the phosphorous epoxy resin system of flame retardant properties excellence just is widely studied since the middle and later periods nineties in last century as the principal item of " Halogen " Resins, epoxy, as patent patent US6403220, US6500546 and EP1312638 etc.But it is big more that the shortcoming of this resinoid system is phosphorus content, and the thermal characteristics of material is just poor more, be difficult to take into account thermotolerance and flame retardant resistance simultaneously, and preparation cost is higher relatively, and industrialization is difficulty relatively.The phosphate ester structure of facile hydrolysis threatens its stable usability in hygrothermal environment in the product in addition.In recent years, the nitrogen flame retardant comes into one's own gradually owing to have advantage such as low toxicity, efficient, high heat resistance.But most nitrogen flame retardants are additive flame retardant, and are poor with the epoxy systems consistency, are difficult to widely apply the epoxy systems that is used for electric field.Patent US20030099839, US6617029 etc. introduce triazine structure (being mainly derived from trimeric cyanamide) in the epoxy systems with the covalent linkage form, be used with phosphorous resin, obtain better flame retardant effect, yet cause fragility to be difficult to adapt to general procedure for processing greatly.The nitrogen-containing epoxy thermoset of the employing introducing unsymmetrical structure method manufacturing that we invent in patent (ZL200410053181.0) can to a certain degree reduce the fragility of high nitrogen-containing epoxy thermoset cured article.Therefore for nitrogenous fire retarding epoxide resin system, improving to satisfy the service requirements of electronic product in the time of the epoxy resin cured product over-all properties, is the research topic that this area needs to be resolved hurrily.
At present electric equipment products needs used resin to have the UV barrier functionality satisfying the procedure for processing requirement as copper-clad plate in addition, and most resin combinations of using at present need add the UV blocking agent, cause the product cost rising.
Summary of the invention:
At problems of the prior art, two amphyls that contain aromatic schiff base structure and fragrant ehter bond provided by the invention, the manufacturing that can be used for making nitrogen-containing epoxy thermoset, combustion-proof epoxide resin composition and be applied to veneer sheet.Use this veneer sheet can take into account the thermotolerance of product, flame retardant resistance and processibility (as the UV block).
The present invention is to realize by such technical scheme for reaching above purpose:
Manufacturing contains the diphenol derivative of aromatic schiff base and diether linkage structure: be starting raw material with the bisphenol compound, obtain diphenol derivative with nitrophenols, hydrazine hydrate and hydroxy benzaldehyde reaction successively.
The feature such as the general expression (1) of dihydric phenols derivative that wherein contains aromatic schiff base and diether linkage structure is represented:
R wherein
1Expression straight chain, branched-chain alkyl, aryl or aralkyl, R is:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Make two amphyls represented, at first will obtain the aromatic diamine derivative that contain aromatic oxide bond structure represented as general expression (2) as general expression (1):
R is in the formula:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Need two-step reaction synthetic as the ether-containing key aromatic diamines that general expression (2) is represented: the one, utilize halogenated nitrobenzene and bisphenol compound and under alkaline condition, prepared in reaction obtains under nitrogen protection and comparatively high temps in polar solvent.Wherein halogenated nitrobenzene is preferably parachloronitrobenzene, p-Nitrobromobenzene, m-chloro-nitrobenzene, a bromo nitrobenzene, o-chloronitrobenzene and o-bromonitrobenzene; Bisphenol compound is preferably the compound of following expression:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, or R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Solvent is preferably dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone and dimethyl sulfone for this reaction is the inert high boiling solvent.Basic catalyst is preferably salt of wormwood, yellow soda ash, saleratus and sodium bicarbonate; The mole proportioning of halogenated nitrobenzene and bisphenol compound reaction is 2～3: 1, is preferably 2～2.5: 1.The consumption of basic catalyst with can with halogenated nitrobenzene equivalent the best; Temperature of reaction is 60-180 ℃, is preferably 130-160 ℃; Reaction times is 5-10 hour, is preferably 8-10 hour.
Another is the reduction of above-mentioned dinitro compound, and the system that any suitable reduction nitro is an amido all is fit to this system, be not particularly limited, but wherein preferable with hydrazine hydrate/iron trichloride/gac system and Raney nickel-hydrogen reducing system.Hydrazine hydrate/iron trichloride/gac the system that adopts, wherein hydrazine hydrate is the aqueous solution of hydrazine, its weight percent concentration is 10-90wt%, be preferably 50-85wt%, hydrazine hydrate need be excessive during use, its molar equivalent be dinitro compound 2-10 doubly, preferred 2-4 is doubly preferable, the adding method of hydrazine hydrate is preferably progressively addition method to avoid its too much hydrolysis.The iron trichloride consumption is the 0.1-10wt% of dinitro compound weight, and activated carbon dosage is the 0.1-10wt% of dinitro compound weight.The solvent that uses is the solvent to this reactionlessness, is mainly alcohols and cyclic ethers class, and alcohols is preferably methyl alcohol, ethanol, propyl alcohol and butanols; The cyclic ethers class is preferably tetrahydrofuran (THF), dioxane.Temperature of reaction is 0-120 ℃, is preferably 50-110 ℃; Reaction times is 2-10 hour, is preferably 4-6 hour.The aromatic diamine derivative of gained recrystallization in methyl alcohol, ethanol or dioxane can obtain pure compound.Raney nickel-hydrogen reducing the system that adopts, wherein Raney nickel and hydrogen all can be buied, and get final product according to the routine operation method of this method.
The aromatic diamines that contains fragrant ehter bond of above-mentioned preparation and following general expression (3):
R in the formula
1Expression straight chain, branched-chain alkyl, aryl or aralkyl.
The hydroxy benzaldehyde reaction of expression can make two amphyls that contain aromatic schiff base and diether linkage structure represented as general expression (1).Reaction solvent is the solvent to this reactionlessness, can be methyl alcohol, ethanol, propyl alcohol, butanols, tetrahydrofuran (THF), dioxane, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfone etc., is preferably ethanol, dioxane and dimethyl formamide.This reaction also can be used acid as catalyst, with zinc chloride, more excellent to the acid of methylbenzene semi-annular jade pendant.Temperature of reaction is generally 0-150 ℃, is preferably 20-100 ℃.Reaction times is 0.5-24 hour, is preferably 4-6 hour.After reaction finishes, filtration, the dry goods that form.Also can utilize process for purification commonly used to make with extra care as required.
Can produce two amphyls that contain aromatic schiff base and diether linkage structure of described general expression (1) expression thus, this derivative has the phenolic group hydroxyl.The invention provides a kind of its method of making nitrogen-containing epoxy thermoset of using, promptly be to make itself and epoxy compounds direct reaction, or itself and epoxyhalopropane are reacted under alkaline condition.
Below nitrogen-containing epoxy thermoset provided by the invention and manufacture method thereof are described.
The bicyclic oxygen compound that is characterized as the structural unit that contains described general expression (4) expression of nitrogen-containing epoxy thermoset of the present invention:
R wherein
1Expression straight chain, branched-chain alkyl, aryl or aralkyl, R is:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Method as the structural unit of introducing described general expression (4) expression has: two amphyls that contain fragrant ehter bond and schiff base structure of described general expression (1) expression and functionality are more than or equal to the direct chain extending reaction of 2 epoxy compounds (hereinafter referred to as implementation method 1), or two amphyls that contain fragrant ehter bond and schiff base structure reaction (hereinafter referred to as implementation method 2) under basic catalyst exists that described general expression (1) is represented.
Implementation method 1: wherein said epoxy compounds comprises Racemic glycidol ethers monomer and the oligopolymer that contains 2 epoxy group(ing) in 1 molecule at least, as: bisphenol type epoxy, tetrabromo-bisphenol type epoxy, Bisphenol F type epoxy, bisphenol S type epoxy, biphenyl type epoxy, naphthalene type epoxy, ortho-cresol type phenolic aldehyde epoxy, phenol type phenolic aldehyde epoxy, bisphenol A-type phenolic aldehyde epoxy, bromination phenolic aldehyde epoxy, diglycidyl ether of ethylene glycol and propanetriol-diglycidyl-ether etc., aromatic amine and nitrogen heterocyclic derive two N-Racemic glycidol amine monomer and oligopolymer, for example: N, N '-diglycidylaniline, triglycidyl group isourea cyanates etc. also can be above-mentioned several mixing.The reaction mole proportioning of described general expression (1) expression diphenol derivative and epoxy compounds is generally and is 0-1: 1, be preferably 0.1-0.5: 1.Temperature of reaction is generally 0-200 ℃, is preferably 60-180 ℃, and the reaction times is 0.5-12 hour, is preferably 2-6 hour.Reaction also can be carried out in the presence of catalyzer, is preferably organic alkali catalyst, and is Phosphorus as triphenyl phosphorus, three (2, the 6-Dimethoxyphenyl) phosphorus etc., tertiary amines such as phenyl dimethylamino, ammonium salt classes such as tetraethylammonium bromide, benzyl trimethyl ammonium chloride etc.Be reflected at and carry out under the vacuum condition obtaining better reaction result.Also can use solvent according to reaction, spendable solvent for example has: halo alkanes such as chloroform, methylene dichloride, N-Methyl pyrrolidone, dimethyl formamide, dioxane etc.The gained nitrogen-containing epoxy thermoset is generally yellow powder shape solid, and molecular weight is generally 500-2000.
Implementation method 2:
Described epoxyhalopropane is epoxy chloropropane, epoxy bromopropane, methyl epichlorohydrin, is preferably epoxy chloropropane cheap and easy to get.The usage quantity of epoxyhalopropane is generally normal 2～20 times of diphenol derivative of described general expression (1) expression.Used basic catalyst is if any inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, triethylamine, Trimethylamine 99, N, N '-dimethylcyclohexylamine, pyridine, 2-picoline, 4-picoline, to dimethylamino pyrrole, Tetraethylammonium bromide, benzyl trimethyl ammonia chloride etc., can mix use, have no particular limits.The usage quantity of alkali must make the phenolic hydroxyl group activation of the diphenol derivative of described general expression (1) expression, and can eliminate the by-product hydrogen halide that reaction generates.The 1-10 that common alkali consumption is the phenolic hydroxyl group number doubly.Use mineral alkali such as sodium hydroxide and quaternary ammonium salt such as Tetraethylammonium bromide to be used, can obtain preferable reaction effect, in the case, the usage quantity of quaternary ammonium salt is 0.1～2mol% of phenolic hydroxyl group.Reaction is solvent usually with the epoxyhalopropane, also can add other inert solvent as required.Temperature of reaction is generally 30-120 ℃; Be preferably 80～120 ℃.Reaction times is generally 0.5～24 hour, is preferably 0.5～5 hour.After reaction finished, the nitrogen-containing epoxy thermoset that is generated was dissolved in toluene, the methylene dichloride equal solvent, makes with extra care by methods such as washing, distillations.The nitrogen-containing epoxy thermoset that obtains is yellow thick liquid or solid, and molecular weight is 300～1500.
It is a kind of by the application of described general expression (1) expression diphenol derivative with the nitrogen-containing epoxy thermoset of the diphenol derivative modular construction that contains described general expression (4) expression that uses its manufacturing that the present invention also provides.Promptly be to form combustion-proof epoxide resin composition, and be used for the manufacturing of veneer sheet with Resins, epoxy, solidifying agent, curing catalyst, fire retardant and solvent etc.
Fire-retarded epoxy resin constituent of the present invention is characterised in that: contain by a kind of of described general expression (1) expression diphenol derivative at least or contain a kind of by in the nitrogen-containing epoxy thermoset of the diphenol derivative modular construction of described general expression (4) expression.Its composition of fire-retarded epoxy resin constituent provided by the invention and content are:
Resins, epoxy: 20～80 parts (in constituent solid content);
Solidifying agent: 1～80 part (in constituent solid content);
Curing catalyst: 0.01～2wt.% of resin total solid content;
Fire retardant: 0～40wt.% of weight resin;
Solvent: 15～60wt.% of resin total solid content.
Described Resins, epoxy is except nitrogen-containing epoxy thermoset provided by the present invention, also comprise all Resins, epoxy well known in the art, as contain brominated Resins, epoxy such as tetrabromo-bisphenol type Resins, epoxy, brominated phenols formaldehyde epoxy resin, contain annular phosphate group (as following formula 5-8) and contain the phosphorous epoxy resin of phosphine structure (as following formula 9-10):
R
5＝H，-CH
3 X＝A or B (8)
Or general commercial Resins, epoxy such as bisphenol type epoxy, Bisphenol F type epoxy, bisphenol S type epoxy, biphenyl type epoxy, naphthalene type epoxy, ortho-cresol type phenolic aldehyde epoxy, phenol type phenolic aldehyde epoxy, bisphenol A-type phenolic aldehyde epoxy.The use of above-mentioned Resins, epoxy is not particularly limited, and also can be wherein several mixing as required.
Described solidifying agent can use all materials well known in the art except diphenol derivative provided by the invention.Particularly: aromatic amine such as mphenylenediamine, Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4,4 '-diamino diphenyl sulfone etc., phenolic solidifying agent such as phenol molded lines resol, cresols molded lines resol, bromination linear phenolic resin and bisphenol A-type linear phenolic resin, and Dyhard RU 100, cyanurotriamide modified novolac phenolic aldehyde etc.Above-mentioned solidifying agent can be used alone, but also also mix together.The usage quantity of described solidifying agent preferably adds according to total epoxy equivalent (weight) of used Resins, epoxy.
Described curing catalyst uses all materials well known in the art.Be preferably glyoxaline compound, triphenyl phosphorus etc. such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
Described solvent uses all materials well known in the art.As toluene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, acetone, pimelinketone, Propylene Glycol Dimethyl Ether etc.These solvents can use separately also can mix use.
Described fire retardant uses all materials well known in the art, and the present invention is preferably hydrated metal oxide, as aluminium hydroxide, magnesium hydroxide and nitrogenous or phosphorus type flame retardant, as melamine derivative, phosphoric acid ester derivant, ammonium polyphosphate.
Combustion-proof epoxide resin composition of the present invention can be used for the manufacturing of veneer sheet.Fire-retarded epoxy resin constituent provided by the invention is mixed with the epoxy resin adhesive liquid that solid content is 40-85%, with the alkali-free glass cloth is strongthener, by impregnation, semicure and heat pressing process compacting, obtain woven fiber glass enhanced epoxy matrix composite, i.e. veneer sheet.Wherein said solvent uses all materials well known in the art, is preferably to be toluene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, acetone and pimelinketone etc., and these solvents can use separately also can mix use.
Remarkable advantage of the present invention and effect:
The present invention is from the angle of molecular structure, two amphyls or the Resins, epoxy that design, synthesized a class rigid chain segment (aromatic oxide bond structure) and hard and soft segment (being the aromatic schiff base structure) and deposit, and with component epoxy constituents such as Resins, epoxy, solidifying agent, curing catalyst, obtain epoxy resin cured product fire-retardant, heat-resisting and that processing characteristics is excellent by simple, economic preparation route, and be applied to the making of veneer sheet.
Embodiment:
Utilize embodiment to describe the present invention in detail below, the present invention is not limited to this.
Embodiment 1:2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane:
Synthetic:
With 0.1mol dihydroxyphenyl propane, 0.22mol parachloronitrobenzene, 0.22mol K
2CO
3, 200ml DMF adds in the 500ml four-hole boiling flask, under nitrogen protection, stirring heating is warming up to 145-150 ℃ of constant temperature back flow reaction 10h.After reaction finishes while hot vacuum filtration remove impurity such as inorganic salt, slowly add the 80ml deionized water, have yellow solid to separate out after the cooling, vacuum filtration uses deionized water and washing with alcohol for several times more successively, vacuum-drying gets the khaki color powdery solid.With synthetic dinitrobenzene product, 200ml ethanol, 2.0g gac and 0.6g FeCl above the 0.1mol
36H
2O adds flask successively, and the preheating certain hour is warming up to 80 ℃.The hydrazine hydrate solution of 60ml 85wt.% slowly is added dropwise to system, drips off back isothermal reaction 4h.Filtered while hot is removed inorganic salt and gac, filtrate is cooled off gradually again, separates out precipitation.To precipitate and use ethyl alcohol recrystallization, vacuum-drying gets yellow needle-like crystal, obtain containing the aromatic diamine compound of ehter bond, the 0.10mol diamines is dissolved in DMF, and join in the constant pressure funnel, the 0.21mol p-Hydroxybenzaldehyde is added four-hole boiling flask, add ethanol, in N
2Atmosphere slowly stirs, and is heated to when refluxing to begin to drip above-mentioned two amine aqueous solutions, and about 1h drips off.Dropwise the back and continue isothermal reaction 6-8h, reaction soln is poured in the 1000ml deionized water, get yellow mercury oxide.Leave standstill, suction filtration gets yellow powdery solid, and recrystallization in dehydrated alcohol obtains target product, productive rate 95%.Yield:95%, mp:125～127 ℃; IR (KBr, cm
-1): 3415 (Ar-OH), 1604 (CH=N), 1235 (Ar-O-Ar). ultimate analysis: C
41H
46N
2O
4(618.7): Cal:C, 79.59%; H, 5.54%, N, 4.53%; Found:C, 79.04%; H, 5.85%, N, 4.56%.
Embodiment 2:1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene:
Synthetic:
Replace dihydroxyphenyl propane with Resorcinol, reaction obtains yellow powder shape solid.Productive rate: 97%.M.p.278～280 ℃; IR (KBr, cm
-1): 3368 (Ar-OH), 1605 (HC=N), 1245 (Ar-O-Ar). ultimate analysis: C
32H
24N
2O
4(500.6): Cal:C, 76.79%; H, 5.83%, N, 5.60%; Found:C, 76.04%; H, 4.98%, N, 5.63%.
Embodiment 3: the diphenol that contains phthalazone/schiff bases structure:
Synthetic:
With 23.8g phthalazone (0.10mol), 34.6g parachloronitrobenzene (0.22mol), 31.0g salt of wormwood (0.22mol) join in the 500ml four neck flasks, and 150ml DMF makes solvent, N
2Following stirring and dissolving.Be warming up to boiling reflux (about 145-150 ℃) then, keep back flow reaction 8～10h.Be cooled to room temperature then, with product pour into water/ethanol (50/50, v/v) wash in the mixing solutions, suction filtration gets yellow solid, for containing the dinitro compound of naphthyridine ketone structure, recrystallization in the ethanol.With 48.0g previous step synthetic dinitrobenzene product D NP (0.1mol), 1.50g gac, 0.6g FeCl
36H
2O and 300ml dioxane add flask successively, rise to reflux temperature.Hydrazine hydrate solution with 60ml 85wt.% slowly drops in the flask then, isothermal reaction 4h again after 2h drips.Filtered while hot is fallen inorganic salt and gac, filtrate is cooled off gradually again, separates out precipitation, filter crude product.Recrystallization in dioxane/water then obtains containing the aromatic diamines of naphthyridine ketone structure.With the above-mentioned diamines of 0.1mol, the ZnCl of 4-hydroxy benzaldehyde and catalytic amount
2Join in the 500ml four-hole boiling flask, 150ml adds solvent DMF,, after 8 hours product solution is poured in the big water gaging in 100 ℃ of following stirring reactions, obtains the khaki color throw out.Leave standstill suction filtration and get yellow powdery solid.Recrystallization gets target product in the DMF/ ethanol.Productive rate is 95wt.%, mp:304～306 ℃.IR(KBr，cm
-1)：3369(Ar-OH)，1646(C＝O)，1626(C＝N)，1235(Ar-O-Ar，Ar-OH)。C
40H
28O
4N
4(628.7)：Cal：C，76.42％；H，4.49％，N，8.91％；Found：C，76.55％；H，4.40％，N，8.99％。
Embodiment 4: by 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane and the synthetic nitrogen-containing epoxy thermoset of epichlorohydrin reaction.
Take by weighing 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 10.0g, add in the 50g epoxy chloropropane, after being heated to dissolving, add the 0.1g benzyl trimethyl ammonium chloride again, keep temperature of reaction in 90 ℃ after about 30 minutes, with the 1.68g dissolution of sodium hydroxide in 3.0ml water, be divided into three batches, every interval joined in the reaction system in 10 minutes.Then in about 100 minutes of 90 ℃ of reactions.Most of epoxy chloropropane is removed in decompression, the cooling after washing, joins in a large amount of methyl alcohol and obtains yellow solid.Productive rate: 80%.Molecular weight 400-900, IR (KBr, cm
-1): 3400 (OH), 1624 (C=N), 1240 (aryl oxide keys), 911 (epoxide groups).
Embodiment 5: by 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene and epichlorohydrin reaction synthesize nitrogen-containing epoxy thermoset.
Synthetic method is with embodiment four.Product is a yellow solid.Molecular weight 400-1000, IR (KBr, cm
-1): 3330 (OH), 1620 (C=N), 1240 (aryl oxide keys), 911 (epoxide groups).
Embodiment 6: by 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } methane and the synthetic nitrogen-containing epoxy thermoset of Resins, epoxy chain extending reaction
Take by weighing 2 respectively, the triphenyl phosphorus of 2 '-two { 4-[4-(hydroxyl) phenyl Schiff base] phenol oxygen base phenyl } methane 30g, 100g E51 and 0.1wt.%, add and be equipped with in the three-necked bottle of thermometer, agitator and vacuum system coupling device, vacuumize in the bottle (740～750mmHg) and slow heated and stirred, 100 ℃ of following heating under vacuum to eliminate the small molecular weight impurity in the system.Diphenol is dissolved in the Resins, epoxy gradually simultaneously, and when no bubble, beginning slowly is warming up to 140 ℃, reacts 2 hours.Obtain being the nitrogen-containing epoxy thermoset of red solid under the normal temperature, molecular weight is about 500, and is suitable with calculated value.This reaction can dimethyl formamide be that solvent reacts also, and the gained reactant solution can be directly used in configuration fire retarding epoxide resin glue.Molecular weight 600-2000.IR (KBr, cm
-1): 1622 (C=N), 1240 (aryl oxide keys), 912 (epoxide groups).
Embodiment 7: by the diphenol and the epichlorohydrin reaction synthetic epoxy resin of phthalazone/schiff bases structure.
Synthetic method is with embodiment four.Product is a yellow solid.Molecular weight 600-1500.IR (KBr, cm-1): 3330 (OH), 1646 (C=O), 1626 (C=N), 1240 (aryl oxide keys), 915 (epoxide groups).
Combustion-proof epoxide resin composition
Embodiment 8: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 30g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 40g, 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 23.8g, 2,2 '-two [4-(amino) phenyl phenol oxygen base] propane: 31.6g, solvent is the mixing solutions of dimethyl formamide and acetone, makes solid content and be 60% glue.
Embodiment 9: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 38g, phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.32g/eq) 25g, 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 43g, 2,2 '-two [4-(amino) phenyl phenol oxygen base] propane: 21.3g, solvent is an acetone, makes solid content and be 60% glue.
Embodiment 10: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 35g, phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.32g/eq) 23g, 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 59.2g, 2,2 '-two [4-(amino) phenyl phenol oxygen base] propane: 13g, solvent is an acetone, makes solid content and be 60% glue.
Embodiment 11: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 30g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 50g, 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 22g, 1,4-two (p-aminophenyl oxygen base) benzene: 25.7g, solvent is a dimethyl formamide, makes solid content and be 55% glue.
Embodiment 12: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 35g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 35g, 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 38.5g, 1,4-two (p-aminophenyl oxygen base) benzene: 16.8g, solvent is a dimethyl formamide, makes solid content and be 55% glue.
Embodiment 13: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 45g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 20g, 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 54g, 1,4-two (p-aminophenyl oxygen base) benzene: 10.5g, solvent is a dimethyl formamide, makes solid content and be 55% glue.
Embodiment 14: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 20g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 50g, the diphenol 24g that contains phthalazone/schiff bases structure, the diamines that contains phthalazone/schiff bases structure: 32.5g, solvent is an acetone, makes solid content and be 55% glue.
Embodiment 15: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 32g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 30g, the diphenol 43g that contains phthalazone/schiff bases structure, the diamines that contains phthalazone/schiff bases structure: 21.5g, solvent is an acetone, makes solid content and be 50% glue.
Embodiment 16: phosphorous phenol type novolac epoxy (epoxy equivalent (weight) 0.35g/eq) 65g, and 2,2 '-two { 4-[4-(hydroxyl) phenyl Schiff base] phenol oxygen base phenyl } propane 56g, solvent is a dimethyl formamide, makes solid content and be 60% glue.
Embodiment 17: phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.35g/eq) 67g, and 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 47g, solvent is a dimethyl formamide, makes solid content and be 45% glue.
Embodiment 18: phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.35g/eq) 85g, contain the diamines 32g of phthalazone/schiff bases structure, and solvent is a dimethyl formamide, makes solid content and be 40% glue.
Embodiment 19: phosphorous ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 80g, by embodiment 4 synthetic nitrogen-containing epoxy thermoset 20g, be dissolved in the dimethyl formamide, and add carbamide-phenol Lip river furac solidifying agent 17g, be 55% adding butanone adjusting glue solid content.
Embodiment 20: phosphorous ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 80g, by embodiment 5 synthetic nitrogen-containing epoxy thermoset 20g, be dissolved in the dimethyl formamide, and add carbamide-phenol Lip river furac solidifying agent 17g, be 55% adding butanone adjusting glue solid content.
Embodiment 21: phosphorous ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 80g, by embodiment 7 synthetic nitrogen-containing epoxy thermoset 20g, be dissolved in the dimethyl formamide, and add cyanurotriamide modified novolac phenolic aldehyde (laboratory is from synthetic) 17g, be 60% adding butanone adjusting glue solid content.
It is the epoxy resin adhesive liquid of 40-85% that the foregoing description 8-18 is become solid content by formulated, with alkali-free 7628 type woven fiber glass is strongthener, (the prepreg solid content is controlled at 38～45wt.%) by impregnation, semicure, in the vacuum hotpressing machine,, obtain woven fiber glass enhanced epoxy matrix composite in 175 ℃ of compacting 2.0h.The naturally cooling depanning obtains the sample of long 130mm * wide * 13mm * thick 1.6mm after cutting out, carry out the experiment of oxygen index and vertical combustion, utilizes the second-order transition temperature of DSC method test cured article, the results are shown in Table 1.
Composition epoxy resin in the foregoing description does not need to add the UV blocking agent, can reach UV barrier functionality preferably, and prepared double-sided copper-clad paper tinsel plate adapts to whole procedure for processing of printed circuit board fully.
Table 1
| Embodiment | Second-order transition temperature (℃, DSC) | Oxygen index (LOI) | Vertical combustion (UL94) |
| 8 9 10 11 12 13 14 15 16 17 18 19 20 21 | 153 146 139 147 136 125 153 156 157 135 157 174 165 185 | 28.8 30.5 33.0 26.4 28.5 31.6 30.8 31.2 29.0 28.5 35.8 34.5 33.0 36.0 | V-0 V-0 V-0 V-1 V-0 V-0 V-0 V-0 V-1 V-1 V-0 V-0 V-0 V-0 |
Claims (10)
1. contain aromatic schiff base base and diether linkage structure diphenol derivative, it is characterized in that, this diphenol derivative can be represented by following general expression (1):
R wherein
1Expression straight chain, branched-chain alkyl, aryl or aralkyl, R is:
Wherein, (a) in X be-,-C (CH
3)
2-,-SO
2-,-CH
2-With-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
2. the manufacture method that contains aromatic schiff base and diether linkage structure diphenol derivative of the described general expression of claim 1 (1) expression, it is characterized in that: by the aromatic diamine of general expression (2) expression with carry out the equivalent addition-elimination reaction by the hydroxy benzaldehyde of general expression (3) expression and obtain, temperature of reaction is 0-150 ℃, and the reaction times is 0.5-24 hour.
R is in the formula:
Wherein, (a) in X be-,-C (CH
3)
2-,-SO
2-,-CH
2-With-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl,
R in the formula
1Expression straight chain, branched-chain alkyl, aryl or aralkyl.
3. the described application that contains aromatic schiff base and diether linkage structure diphenol derivative of claim 1 is used to make nitrogen-containing epoxy thermoset.
4. by the described application that contains aromatic schiff base and diether linkage structure diphenol derivative of claim 3, it is characterized in that nitrogen-containing epoxy thermoset is to contain as the described modular construction bicyclic oxygen of general formula (4) compound,
R wherein
1Expression straight chain, branched-chain alkyl, aryl or aralkyl, R is:
Wherein, (a) in X be-,-C (CH
3)
2-,-SO
2-,-CH
2-With-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
5. by the described application that contains aromatic schiff base and diether linkage structure diphenol derivative of claim 3, when it is characterized in that making nitrogen-containing epoxy thermoset, by two amphyls of general expression (1) expression and functionality more than or equal to 2 epoxy compounds under the vacuum condition under 0-200 ℃ temperature chain extending reaction, the reaction mole proportioning of diphenol derivative and epoxy compounds is 0-1: 1, and the reaction times is 0.5～12 hour.
6. by the described application that contains aromatic schiff base and diether linkage structure dihydric phenol of claim 3, it is characterized in that, two amphyls that make described general expression (1) expression under basic catalyst exists with the reaction of epoxyhalopropane, the usage quantity of epoxyhalopropane is normal 2～20 times of the diphenol derivative of described general expression (1) expression, basic catalyst is oxyhydroxide, organic amine, organic phosphine and the quaternary ammonium salt of basic metal and alkaline-earth metal, temperature of reaction is 30-120 ℃, and the reaction times is 0.5～24 hour.
7. by the described application that contains aromatic schiff base and diether linkage structure diphenol derivative of claim 3, described nitrogen-containing epoxy thermoset is used to make the fire-retarded epoxy resin constituent.
8. by the described application that contains aromatic schiff base and diether linkage structure diphenol derivative of claim 7, it is characterized in that: described fire-retarded epoxy resin constituent, by containing by a kind of of described general expression (1) expression diphenol derivative at least or containing by a kind of composition the in the nitrogen-containing epoxy thermoset of the diphenol derivative modular construction of described general expression (4) expression, the component of this constituent and constituent solid content are as follows:
Resins, epoxy accounts for the constituent solid content: 20～80 parts;
Solidifying agent accounts for the constituent solid content: 1～80 part;
Curing catalyst: 0.01～2wt.% of resin total solid content;
Fire retardant: 0～40wt.% of weight resin;
Solvent: 15～60wt.% of resin total solid content.
9. the described application that contains aromatic schiff base and diether linkage structure diphenol derivative of claim 3 is used for the making layer pressing plate.
10. by the described application that contains aromatic schiff base and diether linkage structure diphenol derivative of claim 9, it is characterized in that being mixed with the epoxy resin adhesive liquid that solid content is 40-85%, with the alkali-free glass cloth is strongthener, by obtaining veneer sheet after impregnation, semicure and the hot pressing.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193673A (en) * | 2013-03-19 | 2013-07-10 | 淮海工学院 | Quaternary ammonium salt (salicylidene amino acid) supported functional ligand and preparation method thereof |
| CN103193701A (en) * | 2013-03-14 | 2013-07-10 | 淮海工学院 | Functional ligand and preparation method thereof |
| CN107349868A (en) * | 2016-05-10 | 2017-11-17 | 中日合成化学股份有限公司 | Method for producing surfactant and use thereof |
| CN107814911A (en) * | 2017-09-19 | 2018-03-20 | 中山大学 | A kind of Intrinsical selfreparing hyperbranched epoxy resin and its preparation method and application |
| CN114907213A (en) * | 2022-05-09 | 2022-08-16 | 河北海力香料股份有限公司 | Preparation method of high-quality p-chloronitrobenzene |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066765A (en) * | 1990-04-11 | 1991-11-19 | Nippon Steel Chemical Co., Ltd. | Poly(azomethine-ester) having film-forming ability, and heat resistance pre and regulated monomer sequences in the polymer backbone |
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2006
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193701A (en) * | 2013-03-14 | 2013-07-10 | 淮海工学院 | Functional ligand and preparation method thereof |
| CN103193673A (en) * | 2013-03-19 | 2013-07-10 | 淮海工学院 | Quaternary ammonium salt (salicylidene amino acid) supported functional ligand and preparation method thereof |
| CN103193673B (en) * | 2013-03-19 | 2014-07-23 | 淮海工学院 | Quaternary ammonium salt (salicylidene amino acid) supported functional ligand and preparation method thereof |
| CN107349868A (en) * | 2016-05-10 | 2017-11-17 | 中日合成化学股份有限公司 | Method for producing surfactant and use thereof |
| CN107349868B (en) * | 2016-05-10 | 2019-07-12 | 中日合成化学股份有限公司 | Method for producing surfactant and use thereof |
| CN107814911A (en) * | 2017-09-19 | 2018-03-20 | 中山大学 | A kind of Intrinsical selfreparing hyperbranched epoxy resin and its preparation method and application |
| CN107814911B (en) * | 2017-09-19 | 2020-04-10 | 中山大学 | Intrinsic self-repairing hyperbranched epoxy resin and preparation method and application thereof |
| CN114907213A (en) * | 2022-05-09 | 2022-08-16 | 河北海力香料股份有限公司 | Preparation method of high-quality p-chloronitrobenzene |
| CN115558185A (en) * | 2022-10-17 | 2023-01-03 | 安徽杰蓝特新材料有限公司 | HDPE hollow wall winding pipe |
| CN115558185B (en) * | 2022-10-17 | 2023-09-05 | 安徽杰蓝特新材料有限公司 | HDPE hollow wall winding pipe |
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