Technical background
Resins, epoxy has good insulation performance, thermotolerance, chemical resistance, mechanical property and to the over-all propertieies such as cementability of various base materials; and after thermofixation; its shrinking percentage is significantly less than other thermosetting resin usually; thereby as composite matrix resin, packaged material, fiber reinforced material, insulation protection material etc.; by method machine-shapings such as casting, dipping, transfer mould, winding, laminations, be widely used in electric industrial circle.
As everyone knows, the equipment that uses in the electric field develops rapidly towards miniaturization, lightweight, thin typeization, densification direction.For the macromolecular material that uses in various device, performance must improve constantly, and to adapt to the demand for development of microelectronics, guarantees that electronics can steady running in various environment.
The high performance of Resins, epoxy is the problem that numerous researchists pay special attention in the recent period.As matrix resin, its high performance comprises the raising of every main heat, mechanical index, and the improvement of processing technology.Processing technology is meant the solubility property of resin in solvent, to changing conditions of inorganic substrate wettability of the surface, flowability (suitable viscosity or melt viscosity), solidification process medium viscosity etc.In short, obtain a kind of have both high heat resistance (high glass-transition temperature, Tg) and good solubility and low-viscosity epoxy resin be that the inventor wishes the target that reaches.
Yet, with regard to Resins, epoxy, the raising of thermal property usually and workabilities such as its resolvability, melt viscosity be inverse relationship.That is, if improve its Tg with the method for introducing big rigid radical on molecular skeleton, may cause its solvability variation in common solvent such as acetone and ethylene glycol monomethyl ether, melt viscosity significantly increases, and is unfavorable for complete processing.Conversely, if introduce some flexible structural unit, the viscosity (melt viscosity) of Resins, epoxy is reduced greatly as to dimethylene biphenyl, the mobile improvement, and favorable solubility in general solvent, but unfavorable to the thermotolerance that improves resin like this, its Tg is less than 150 ℃.The work of these aspects existing many researchists reported, U.S.Pat.5 for example, 780,571 (1998), U.S.Pat.5,827,908 (1998), all related to Resins, epoxy among Chinese invention patent CN1106194A and the CN1160724A with above-mentioned similar structures.Also there is the problem that costs an arm and a leg simultaneously in resin like this.
Same well knownly be, the common viscosity of cycloaliphatic epoxy resin is very low, and dielectric properties are good and stable.In the recent period a lot of research work utilize these fundamental characteristics exactly, by introducing the method for other group, further improve its thermal characteristics and other application performance.
Adducible example comprises: propose to make alicyclic olefin glycol and halo cycloolefin carry out etherification reaction among the Chinese invention patent CN1340504A and obtain alicyclic alkatrienes ether compound, use the peroxy acid oxidation then, obtain the epoxide of that include cycloaliphatic hydrocarbons structure, use anhydride type curing agent can make the Tg of cured article reach 180 ℃; Similarly, Chinese invention patent CN1340506A is by generating the coupling of halo cycloolefin alicyclic diolefine, alicyclic monoolefine pure and mild halo cycloolefin etherification reaction or with alicyclic monoolefine dehydration of alcohols synthesis of alicyclic diolefine etherate, reoxidize afterwards, can obtain a kind of viscosity and only be the liquid-state epoxy resin of 40-88mPa.s 25 ℃ of following viscosity, it solidifies back Tg is 150-166 ℃; U.S.Pat.5,312,878 (1994) disclose with containing the unitary resol of dicyclopentadiene structure and have cooperated with the Resins, epoxy that contains naphthalene as solidifying agent, and to improve liquidity, the Tg of cured article is 158-167 ℃; U.S.Pat.4,390,680 disclosed by phenol or derivatives thereof and dicyclopentadiene and other diolefine prepared in reaction phenol-hydrocarbon resin and and then prepare the method for Resins, epoxy, it is higher to obtain resin toughness, heat-drawn wire (HDT) reaches 150-160 ℃.
Can find that from above description by suitable molecular designing, synthetic Resins, epoxy with ad hoc structure truly has and may improve its performance, solves the contradictory relation of thermal property and processibility, realizes the balance of various characteristics.
Inventor of the present invention gains enlightenment from the research work that these reference have been finished just, expectation overcomes the single structure modification that prior art relates to and causes shortcoming on the Resins, epoxy performance, proposition utilizes some to be easy to get, inexpensive, contain the alicyclic olefin of two or more non-conjugated carbon-to-carbon double bonds and the compound that contains naphthyl that is easy to get equally in the molecular structure, by easier method, prepare in a kind of molecular skeleton and not only contain the inflexible naphthylene group but also the bigger alicyclic hydrocarbon structural unit of volume is arranged, the Resins, epoxy of the more shallow excellent property of color and luster, thus the present invention finished.
Summary of the invention
The purpose of this invention is to provide in a kind of molecular skeleton with ad hoc structure and contain naphthalene and the unitary Resins, epoxy of alicyclic hydrocarbon, it is very easily dissolving in common solvent such as acetone, ethylene glycol monomethyl ether, color and luster is more shallow, normal temperature is down for liquid, has good heat-resistant after the curing, in electronics, electrical industry field, can be used as matrix resin heat-resisting, insulativity and use.
Another object of the present invention provides the inexpensive monomer that a kind of utilization is easy to get, and prepares the method for this resin by easier method.
The invention provides and contain naphthalene and the unitary Resins, epoxy of alicyclic hydrocarbon in the following molecular skeleton of structure:
R wherein
1, R
2Be hydrogen, methyl, methoxyl group, sec.-propyl, benzyl, naphthyl, naphthyl methylene, naphthalene propyl group or bromine atoms; G is a glycidyl ether.
The preparation method of this Resins, epoxy at first carries out the carbon-to-carbon condensation reaction by the alicyclic polyene hydrocarbon that contains two or more non-conjugated carbon-to-carbon double bonds in hydroxyl naphthalene compound and the molecular structure in organic solvent in the presence of lewis acid catalyst, wherein the mol ratio of hydroxyl naphthalene compound and alicyclic ring polyene hydrocarbon is 0.5-15, temperature of reaction is 50-180 ℃, reaction times is 2-20 hour, obtains the polynuclear aromatic condenses; This polynuclear aromatic condenses and epoxy chloropropane carry out etherification reaction and can make Resins, epoxy under the alkaline catalysts effect then.
In the preparation method of Resins, epoxy of the present invention, at first prepare the polynuclear aromatic condenses.Promptly in the presence of the Lewis acid of high catalytic activity, the alicyclic polyene hydrocarbon of hydroxyl naphthalene compound and non-conjugated carbon-to-carbon double bond is reacted and make.
Be meant the naphthol compound of naphthols or replacement as the hydroxyl naphthalene compound of the raw material use of preparation polynuclear aromatic condenses among the present invention, also can be to carry out the oligopolymer that condensation reaction obtained by them and aldehyde, ketone or aromatic alcohol, as long as wherein contain a naphthylene group at least, the ortho position or the contraposition of hydroxyl simultaneously has at least one just not to be substituted and can to use.But, carry out in order to help reaction, the substituted radical on the raw material naphthalene nucleus that uses comprises that hydroxyl preferably is no more than two, and substituted radical is sterically hindered little.
The concrete example of hydroxyl naphthalene compound comprises: the 1-naphthols, beta naphthal, 1, the 5-bisnaphthol, 1, the 6-bisnaphthol, 1,1 '-dinaphthol, 5-methyl isophthalic acid-naphthols, 5-methyl-beta naphthal, 5-methoxyl group-1-naphthols, 5-methoxyl group-beta naphthal, 1-bromo-beta naphthal, 6-bromo-beta naphthal, 2-bromo-1-naphthols, 4-bromo-1-naphthols, 5-bromo-1-naphthols, 4-sec.-propyl-1-naphthols, 1-sec.-propyl-beta naphthal, and naphthols-formaldehyde condensation products, naphthols-condensation of acetone thing, naphthols-terephthalyl alcohol condenses, naphthols-P-F condenses or bromide naphthol-formaldehyde condensation products etc., 1-naphthols wherein, beta naphthal, 1,1 '-dinaphthol, naphthols-formaldehyde condensation products, naphthols-condensation of acetone thing or in them two or more mixture be preferred the use.
Alicyclic polyene hydrocarbon mainly is meant to have five yuan or hexavalent ring-type polyene hydrocarbon or condensed ring shape polyene hydrocarbon, contains two unconjugated carbon-to-carbon double bonds in the molecular structure at least.Carbon-to-carbon double bond can be on the same ring, also can be on different rings.Alicyclic polyene hydrocarbon can exist by individual molecule, also can be their oligopolymer.For the consideration of economy and source guarantee, these alicyclic olefins are often obtained by natural product processing.
Therefore, available alicyclic ring polyene hydrocarbon example comprises: limonene, terpinolene, γ-Song Youxi, 1,5-needle juniper diene, 1,6-needle juniper diene, vinyl norbornene, 1,4-cyclohexadiene, zingiberene etc., You Xuan limonene of the present invention, terpinolene, γ-Song Youxi or their mixture.
The reaction of above-mentioned two compounds belongs to Friedel-Crafts alkylation reaction (F-C reaction), in the presence of highly active lewis acid catalyst, can carry out easily, obtain a kind ofly being polynuclear aromatic condenses " bridge ", that several hydroxyl naphthalene compounds are coupled together with alicyclic hydrocarbon.By controlling the mol ratio of two compounds, can regulate the curing characteristics of solubility property, viscosity, molecular weight and the final product Resins, epoxy of polynuclear aromatic condenses within the specific limits.The molar ratio of hydroxyl naphthalene compound and alicyclic olefin can be selected between the scope of 0.5-15.Molar ratio hour, the yield of condensation product is higher, but the ratio that connects 1 alicyclic product on each naphthalene nucleus also can increase, gelation time prolongs when causing final epoxy resin cure, simultaneously the thermal characteristics variation of cured article; Molar ratio surpasses at 15 o'clock, and the molecular weight of condenses is lower, and yield is also lower, is unfavorable for stable on heating raising equally.In the present invention, the molar ratio of hydroxyl naphthalene compound and alicyclic ring polyene hydrocarbon is preferably 3-10.
The lewis acid catalyst that above-mentioned condensation reaction is adopted can comprise: alchlor, aluminum chloride, iron trichloride, tin tetrachloride, titanium tetrachloride, antimony pentachloride, zinc chloride and boron trifluoride and its ether, phenol, amine complex etc.They can directly use, also can be earlier that they are immobilized on ion exchange resin, re-use in condensation reaction afterwards.Consider that from the angle that improves reactive activity and the color and luster that reduces condenses the present invention preferably uses tin tetrachloride, boron trifluoride-ether complex, boron trifluoride-phenol complexes or their mixture.
The usage quantity of lewis acid catalyst can be selected within the specific limits according to the raw material of condensation reaction with to the requirement of condensation reaction time.Among the present invention, its add-on is generally hydroxyl naphthalene compound and alicyclic olefin gross weight 0.05-5wt%, and preferable amount is between the 0.5-3wt%.
This condensation reaction can not carried out in benzene,toluene,xylene, perhydronaphthalene, petroleum naphtha etc. are not participated in the organic solvent of reaction, and the existence of solvent can make reacting balance and evenly carry out, the content of water in the minimizing reaction system that will mention below yet helping.The consumption of solvent in the weight of reaction raw materials hydroxyl naphthalene compound, is 100-400wt% preferably.Setting-up point is preferably 50-180 ℃, when condensation reaction when carrying out greater than 120 ℃ condition, also can not use solvent.According to the variation of temperature of reaction, condensation reaction time is preferably in 2-20 hour scope.
For the F-C reaction, the existence of excess moisture can cause some side reactions, even reaction can't be carried out.Therefore, must remove the moisture of absorption respectively before use, perhaps the way drying by known azeotropic dehydration as hydroxyl naphthalene compound, alicyclic olefin and the solvent of raw material.
The commercially available product of alicyclic polyene hydrocarbon can directly be used.If desired, can remove wherein stopper and other impurity by steps such as alkali cleaning, drying, distillations, use refining back.
There is no particular limitation for the addition sequence of hydroxyl naphthalene compound, alicyclic olefin, lewis acid catalyst, can throw simultaneously to reactor, also can successively add.
In order to obtain the more shallow condensation product of color and luster, the present invention preferably uses rare gas elementes such as exsiccant nitrogen, protective reaction system.
The degree that condensation reaction is carried out can be passed through
1The HNMR spectrum analysis.The chemical shift δ of H in the alicyclic olefin on the non-conjugated carbon-to-carbon double bond is between the 4.7-5.4, differ remarkable with the chemical shift of H on H and the aromatic hydrocarbon ring on the saturated C-C wherein, thereby can be according to the relative intensity judgement alicyclic olefin of fignal center between above-mentioned displacement field and the degree of hydroxyl naphthalene compound condensation reaction, in general, if condensation reaction is carried out fully, this fignal center would not occur.
After reaction is finished, can add alkali lewis acid catalyst was lost efficacy, termination reaction, and then go catalyzer and neutralized reaction product with the distilled water eccysis.Added alkali there is no special qualification, can select alkaline matters such as sodium hydroxide, potassium hydroxide, yellow soda ash, Trisodium Citrate for use, and in being preferably in and the time do not produce the compound of indissoluble.Organic phase places vacuum distillation apparatus, removes solvent, unreacted monomer, thereby obtains the polynuclear aromatic condenses among the present invention.
The molecular weight of polynuclear aromatic condenses can basis
1The relative intensity at the peak that H is corresponding respectively in alicyclic olefin and the hydroxyl naphthalene compound in the HNMR spectrogram is estimated.Also can record, use M by gel permeation chromatograph (GPC)
nExpression number average relative molecular mass.
The polynuclear aromatic condenses that aforesaid method obtains can prepare Resins, epoxy of the present invention according to the method for routine and epichlorohydrin reaction.Specifically, poly-hydroxy can be contained naphthalene compound and be dissolved in the epoxy chloropropane, add sodium hydroxide, potassium hydroxide or other basic catalyst, under 50-120 ℃ of temperature, reacted 1-12 hour, and obtained the compound that contains naphthalene and alicyclic hydrocarbon structural unit of glycidyl ether.
In the present invention, the usage quantity of epoxy chloropropane is excessive, and the molar ratio of itself and polynuclear aromatic condenses is generally 3-20, is preferably 5-15; The molar ratio of alkali and polynuclear aromatic condenses is generally 0.75-1.5, is preferably 0.9-1.3.For reduce final Resins, epoxy hydrolyzable chlorine content, fully the etherification reaction that carries out is necessary.Use phase-transfer catalyst such as etamon chloride, benzyl trimethyl ammonium chloride, line style polyethers such as polyoxyethylene glycol or their mixture among the present invention, promote etherification reaction, its preferred usage quantity is 0.0001-0.01 mole/every mole of polynuclear aromatic condenses.In addition, in order to obtain the more shallow Resins, epoxy of color and luster, in the etherification reaction process, be benchmark with the quality of polynuclear aromatic condenses, generally can use the anhydrous Na of 1-15wt%
2SO
3As reductive agent, its preferable amount 5-10wt%.
Therefore alkaline catalysts joins in the reaction system continuously with the form of the aqueous solution, and reaction is carried out under decompression azeotropic state, constantly takes the water that institute adds water and reaction generation in the alkaline solution by azeotropic out of by epoxy chloropropane.After etherification reaction is finished, by removing by filter excessive alkali and by-product salt, excessive epoxy chloropropane is reclaimed in underpressure distillation, with the resin dissolves that obtains in toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK) or other ketone solvent, the usage quantity of solvent be 3-6 doubly to the weight of primary resin, remove Cl by washing
-And Na
+, washing also can further be removed the impurity that contains hydrolyzable chlorine.Remove solvent under reduced pressure, obtain the very low Resins, epoxy of the present invention of hydrolyzable chlorine content.
Above-mentioned Resins, epoxy can be observed its molecular structure by infrared spectra, in infrared spectrogram, and 910cm
-1The eigen vibration peak of epoxy, 3400cm can appear in the place
-1Near OH base peak can disappear.
Show good thermal property and processing characteristics behind the epoxy resin cure that the present invention obtains, effectively solved the equilibrium problem of various characteristics, promptly when giving the high Tg of resin, high heat resistance, this Resins, epoxy also has lower viscosity, but at the medium good processing characteristics of usual vehicles such as acetone, ethylene glycol monomethyl ether.
Preferred forms
Provide embodiment below and specify the present invention, for expert of the art, these explanations will make the present invention easier to understand.
Embodiment 1
In the reaction flask that thermometer, water trap, prolong and agitator are housed, add 1-naphthols, the beta naphthal of 72g and the toluene of 800mL of 144g, be heated to 115 ℃, stirring and dissolving, backflow 2 hours, be cooled to 40 ℃, the boron trifluoride-ether complex that adds 3mL feeds exsiccant nitrogen, stirs slowly to drip 34g down through refining De limonene, 1.5 hour add, be warming up to 120 ℃ again, continue reaction after 6 hours, cooling.The aqueous sodium carbonate neutralization reaction system that adds 10wt%, and be washed till neutrality with distilled water.Under reduced pressure, reclaim solvent in the organic phase, remove water and unreacted monomer.Obtain 85g polynuclear aromatic condenses, outward appearance is orange-yellow.M
n=430。
Be equipped with in the reaction flask of thermometer, constant flow pump, agitator, water trap and vacuum system at another, add poly-hydroxy naphthalene compound and 300mL epoxy chloropropane that 80g obtains above, stirring and dissolving, pumping into 33g concentration continuously by constant flow pump in reaction flask afterwards in 6 hours is 48% aqueous sodium hydroxide solution, 0.05g etamon chloride and 8g S-WAT, temperature of reaction remains on 60 ℃, pressure remains on-0.085Mpa, refluxes by azeotropic, takes the water in the reaction system out of.After adding alkali lye, continue to react 2 hours under refluxing, remove by filter salt and excessive insolubless such as alkali, behind the unreacted epoxy chloropropane of reclaim under reduced pressure, use 240mL toluene dissolving resin, to neutral, organic phase under reduced pressure removes solvent with hot water wash.Obtain 95g Resins, epoxy of the present invention, outward appearance is faint yellow semisolid, epoxy equivalent (weight) 276g/eq, and dissolving easily in acetone or methyl iso-butyl ketone (MIBK), viscosity 0.11Pas (130 ℃), after being heating and curing with dicyandiamide, 183 ℃ of Tg (DSC method).
Embodiment 2
In the reaction flask that thermometer, water trap, prolong and agitator are housed, add 1 of 143g, the 1-naphthols of 1 '-dinaphthol, 72g and the toluene of 800mL, be heated to 115 ℃, stirring and dissolving, backflow 2 hours are cooled to 40 ℃, add the boron trifluoride-ether complex of 3.5mL, feed exsiccant nitrogen, stir and slowly drip 26g down, added in 1.5 hours, be warming up to 120 ℃ through refining De limonene, continue reaction after 6 hours, cooling.Add 10% aqueous sodium carbonate neutralization reaction system, and be washed till neutrality with distilled water.Under reduced pressure, reclaim solvent in the organic phase, remove water and unreacted monomer.Obtain 75g polynuclear aromatic condenses, outward appearance is orange-yellow.M
n=410。
Be equipped with in the reaction flask of thermometer, constant flow pump, agitator, water trap and vacuum system at another, add poly-hydroxy naphthalene compound and 300mL epoxy chloropropane that 75g obtains above, stirring and dissolving, pumping into 30g concentration continuously by constant flow pump in reaction flask afterwards in 6 hours is 48% aqueous sodium hydroxide solution, 0.03g etamon chloride and 7.5g S-WAT, temperature of reaction remains on 60 ℃, pressure remains on-0.085Mpa, by azeotropic, takes the water in the reaction system out of.After adding alkali lye, continue to react 2 hours under refluxing, remove by filter salt and excessive insolubless such as alkali, behind the unreacted epoxy chloropropane of reclaim under reduced pressure, use 200mL toluene dissolving resin, to neutral, organic phase under reduced pressure removes solvent with hot water wash.Obtain 87g Resins, epoxy of the present invention, outward appearance is faint yellow semisolid, epoxy equivalent (weight) 269g/eq, and dissolving easily in acetone or methyl iso-butyl ketone (MIBK), viscosity 0.06Pas (130 ℃), after being heating and curing with dicyandiamide, 190 ℃ of Tg (DSC method).
Embodiment 3
Except the hydroxyl naphthalene compound being changed into naphthols-formaldehyde condensation polymer beyond the region of objective existence of 230g, all the other operations repeat the step of embodiment 1, obtain 235g polynuclear aromatic condenses, and outward appearance is orange red.M
n=540。
At another thermometer is housed, constant flow pump, agitator, in the reaction flask of water trap and vacuum system, add poly-hydroxy naphthalene compound and 500mL epoxy chloropropane that 100g obtains above, stirring and dissolving, pumping into 55g concentration continuously by constant flow pump in reaction flask afterwards in 6 hours is 48% aqueous sodium hydroxide solution, 0.06g etamon chloride and 10g S-WAT, all the other operations are with the epoxidation reaction step among the embodiment 1, obtain 121g Resins, epoxy of the present invention, outward appearance is a yellow solid, epoxy equivalent (weight) 240g/eq, dissolving easily in methyl iso-butyl ketone (MIBK), viscosity 1.6Pas (130 ℃), after being heating and curing with dicyandiamide, 196 ℃ of Tg (DSC method).