CN101597219A - The active etherate of phenolic compound and preparation thereof - Google Patents
The active etherate of phenolic compound and preparation thereof Download PDFInfo
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- CN101597219A CN101597219A CNA2008100986373A CN200810098637A CN101597219A CN 101597219 A CN101597219 A CN 101597219A CN A2008100986373 A CNA2008100986373 A CN A2008100986373A CN 200810098637 A CN200810098637 A CN 200810098637A CN 101597219 A CN101597219 A CN 101597219A
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Abstract
The present invention relates to general formula (I) compound, wherein variable X and R
1-R
5Such as in the specification sheets definition.The invention still further relates to a kind of method for preparing general formula (I) compound, the method is characterized in that, make as formula (II) compound of etherificate parent or formula (III) compound be selected from vinyl C as etherifying reagent
1-C
6Alkyl oxide and 2, the compound of 3-dihydropyrane is reacting in the double solvents at hydrochloric ether-cyclic ether compounds in the presence of the acid catalyst, its Chinese style (II) and (III) molecular weight of compound between 100～400.General formula of the present invention (I) compound has high acidolysis active at normal temperatures, can be used as to hinder molten/short compound that dissolves in imaging plate-making.
Description
Technical field
The present invention relates to the active etherate and the preparation thereof of phenolic compound.Particularly, the present invention relates to the compound that monobasic, binary or polyphenol compound obtain with the vinyl ether compound etherificate.In addition, the invention still further relates to a kind of method for preparing described active etherate.
Background technology
Positive without preheating thermo-sensitive computer (the computer to plate that directly makes a plate in the past, hereafter is " CTP ") plate adopts the physical change principle more, as the molten effect of the resistance that utilizes background dye and Infrared dyes, or add in addition some can with the material of film forming line style phenol resins generation hydrogen bond association, realize thermo-scan image.Calendar year 2001 the present invention first contriver and the place institute technology that etherate that normal temperature has a high acidolysis active (also claiming the normal temperature chemical amplification type) is made thermal CTP plate material as the molten/chaotropic agent of resistance that begins one's study, and a series of patents (02117827.5 have been applied for, 02160050.3,03143500.9,01123686.8).Be to adopt lower molecular weight polyphenol polycondensate as the etherificate parent except 01123686.8 patent in the patent of being applied for but, most patents are greater than 2000 line style phenol resins, as poly(4-hydroxystyrene) (M with weight-average molecular weight
W=12000) and lacquer resins (M
W=2000～10000) be the etherificate parent, etherifying reagent adopts EVE and dihydropyrane more, and solvent for use is the double solvents system of chloro thing-cyclic ether compounds.This point and former Fuji Photo Film Co., Ltd. be the synthetic resistance of photo-resist molten/method of short molten used single solvent-tetrahydrofuran (THF) have a great difference (a day disclosure special permission communique is flat-10-133378).But owing to use the higher etherificate parent of molecular weight, the etherificate rate generally can not be De Taigao, otherwise too low by the imaging title complex sensitivity of their preparations, also can't carry out alkali smoothly and develop.Even the version base that general using positive PS printing plate sealing of hole is crossed also needs the precoating layer undercoat could solve the dirty problem of keeping on file.The present invention is a background technology with them, use for reference these patent successful experience in the past, draw its advantage, make great efforts to overcome its shortcoming, propose with the lower molecular weight phenolic compound of molecular weight between 100～400 as the etherificate parent, adding is greater than the etherifying reagent of phenolic hydroxyl group mole number, obtains the etherificate rate near 100% etherate as far as possible.So on the one hand the package stability of etherificate product self is greatly improved, the imaging title complex of being prepared on the other hand can obtain the bigger difference solubleness of higher sensitivity and scanning front and back, thereby improved the development latitude significantly, the positive PS printing plate version base of crossing with general sealing of hole can directly be coated with out the good positive without preheating of developing performance thermal CTP plate material, and this also is the present invention and the main difference of conventional art.
Summary of the invention
In view of the above-mentioned problems in the prior art, the invention provides the new compound of a class, the molecular weight for preparing the used phenolic compound of this compound is at 100-400, the etherificate rate is near 100%, described new compound is the etherate that has high acidolysis active at normal temperatures, can be used as the molten/chaotropic agent of resistance in imaging plate-making.
According to a first aspect of the invention, provide following general formula (I) compound,
X is-CH in the formula
2-,
-O-,-S-,
R
1Be-CH
3,-CH
2Cl ,-Ph ,-OC
3H
7Or
R
2Be H, C independently of one another
1-C
4Alkyl or-OR
4, be preferably hydrogen, methyl or-OR
4,
R
3Be H, C independently of one another
1-C
4Alkyl or halogen are preferably hydrogen, methyl, chlorine or bromine,
R
5Be H, C independently of one another
1-C
4Alkyl or halogen are preferably hydrogen, methyl or bromine,
R
4Be C
1-C
6Alkyl-O-CH (CH
3)-or
In preferred embodiments, formula (I) compound is especially for being selected from following compound:
In the present invention, halogen is interpreted as referring to fluorine, chlorine, bromine and iodine, preferred chlorine and bromine.
C
1-C
4Alkyl is interpreted as referring to comprise the straight or branched alkyl of 1-4 carbon atom, and the example comprises methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, preferable methyl and ethyl.
C
1-C
6Alkyl is interpreted as referring to comprise the straight or branched alkyl of 1-6 carbon atom, and the example of this alkyl is C except the preceding paragraph falls
1-C
4Outside cited each alkyl of alkyl, also comprise n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, neo-pentyl, n-hexyl and Sec-Hexyl etc., preferable methyl and ethyl.
According to a second aspect of the invention, provide a kind of method for preparing general formula of the present invention (I) compound, the method is characterized in that:
Work as R
1For-CH
3,-CH
2Cl ,-Ph or-OC
3H
7The time, make following formula (II) compound as the etherificate parent
Perhaps, work as R
1For
The time, make following formula (III) compound as the etherificate parent
Be selected from vinyl C as etherifying reagent
1-C
6Alkyl oxide and 2, and the 3-dihydropyrane (in the present invention, 2, the 3-dihydropyrane is that the two keys of of γ-pyrans are hydrogenated the dihydro-compound that obtains, its structural formula is
) compound reacting wherein variable X and R in the presence of the acid catalyst in the double solvents at hydrochloric ether-cyclic ether compounds
1-R
5Have the implication that provides as above-mentioned mutual-through type (I) compound separately, and formula (II) and (III) molecular weight of compound between 100～400.
In the methods of the invention, use the lower molecular weight phenolic compound as the etherificate parent, this etherificate parent mainly is a bisphenol compound, but also comprises monohydric phenol and polyhydric phenols.Can use 2 in the monohydric phenol compound; the 4-xylenol; 3; the 4-xylenol; p-tert-butylphenol; to chloro-tert.-butylphenol; to benzoyl phenol; 2; 6-dimethyl p-tert-butylphenol; 2; 4; the 6-Trichlorophenol; 2; 4; the 6-tribromophenol; propylparaben; to acetyl phenol; the 4-dihydroxy benaophenonel; p-phenoxyphenol; to thiophenyl phenol; wherein 2; the 4-xylenol; 3, the 4-xylenol; p-tert-butylphenol; to chloro-tert.-butylphenol; to benzoyl phenol; 2,6-dimethyl p-tert-butylphenol; propylparaben; to thiophenyl phenol is that the present invention preferentially recommends the monohydric phenol that uses.Can select 4 for use in the bisphenol compound, 4 '-dihydroxy benaophenonel, 4,4 '-dioxydiphenyl methane (bis-phenol M), 4,4 '-dihydroxyl phenylbenzene sulphur (bisphenol S), 4,4 '-dihydroxy-diphenyl sulfone, dihydroxyphenyl propane, 3,3 '-dichloro bis-phenol M, 3,3 '-dimethyl bis-phenol M, 2,2 '-dimethyl dihydroxyphenyl propane, tetrabromo-bisphenol, tetrabromo-bisphenol s, preferred use 4,4 '-dihydroxy benaophenonel, bis-phenol M, dihydroxyphenyl propane, bisphenol S, 4,4 '-dihydroxy-diphenyl sulfone, 3,3 '-dichloro bis-phenol M and 3,3 '-dimethyl bis-phenol M.Can use following compound in the polyphenol: triphenolyl methane, 1,1,1-triphen phenolic group ethane, 2,6-dihydroxymethyl p-cresol respectively with phenol, meta-cresol, Resorcinol, biphenyl 3 phenol condenses with one to two mol ratio, the present invention preferably uses 2,6-dihydroxymethyl p-cresol two Resorcinols that contract.
In the methods of the invention, use as the molecular weight of all phenolic compounds of etherificate parent all between 100～400.Molecular weight is too big, and the synthetic full ether compound sensitivity that obtains is too low, and short molten ability dies down behind the heat scan, so that it is dirty to be easy to the residual end in the developing process; Molecular weight too hour hinders molten scarce capacity, is easy to subtract the film loss of gloss in the developing process, and it is very narrow that the development latitude becomes.
Its phenol monomer molecule amount of monohydric phenol active etherate with practical value is preferably between 120～180, the ratio of monomeric molecular weight of this phenol and 17 (phenolic hydroxyl group formula weight) and phenolic hydroxyl group number product (abbreviating " M/A value " hereinafter as) is preferably between 8.0～11.0, full etherificate compound molecular weight is preferably between 190～260, between 97～135, the ratio of ether equivalent and M/A value is preferably between 11.5～14.5 for ether equivalent (ratio of ehter bond number in full etherificate compound molecular weight and the molecule).
For the bisphenols active etherate, the monomeric molecular weight of its phenol of most with practical value or better etherates of imaging performance is preferably between 200～300, the M/A value is preferably between 5.6～8, the molecular weight of full ether compound is preferably between 344～444, preferably between 90～110, the ratio of ether equivalent and M/A value is preferably between 12.6～14.6 for the ether equivalent.If consider the more weak phenol of the molten ability of part resistance with 2, the 3-dihydropyrane is done etherifying reagent, and the ratio of ether equivalent and M/A value can be preferably between 12.6～16.5.
For the Polyphenols etherate, the imaging performance M/A of its etherificate parent of etherate preferably is all littler than the value of monohydric phenol and bisphenol compound, and the ether equivalent is also less, and the ratio of ether equivalent and M/A value is then bigger.According to the experience that the contriver summed up in the past, the M/A value of phenolic compound can be used as the sign of judging its short molten ability: promptly generally speaking, the M/A value is more little, and short molten ability is strong more, and the M/A value is big more, and short molten ability is weak more.But for different types of phenolic compound, molecular weight also is an important evidence judging the molten ability of resistance; If M/A is identical, the molecular weight of phenolic compound is more little, and short molten ability is strong more, and molecular weight is big more, and short molten ability is weak more.
In the methods of the invention, the etherifying reagent that is used to prepare described active etherate comprises vinyl C
1-C
6Alkyl oxide and 2, the 3-dihydropyrane.Described vinyl C
1-C
6The example of alkyl oxide comprises EVE, vinyl propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl sec-butyl ether, vinyl tertbutyl ether, vinyl amyl ether and vinyl hexyl ether.Preferred vinyl C
1-C
6Alkyl oxide is vinyl C
1-C
4Alkyl oxide, the example comprise EVE, vinyl propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl sec-butyl ether and vinyl tertbutyl ether.Especially preferred vinyl C
1-C
4Alkyl oxide is an etherifying reagent.In addition, etherifying reagent also can use dihydrofuran or vinyl benzyl ether etc. to have the compound of vinyl ether structure.Consider that from factors such as the source difficulty or ease of reactivity worth and etherifying reagent and prices the present invention recommends to use EVE and/or 2, the 3-dihydropyrane is as etherifying reagent.
Preferably, if etherificate parent molecule amount is higher, the M/A value is bigger, the multiselect EVE, molecular weight is low, the M/A value hour multiselect with 2,3-dihydropyrane and/or vinyl C
3-C
4Alkyl oxide, molten, the short molten ability of the resistance that also takes into account etherate.
The consumption of etherifying reagent is generally 1.2～2.0 times of parent phenolic compound phenolic hydroxyl group mole number, and preferred 1.2～1.5 times, the purpose of excessive use is to guarantee to obtain the etherificate rate near 100% full ether compound.
In the methods of the invention, the acid catalyst that is used for the catalyst etherifying reaction can be selected mineral acid, super acids and/or strong organic acid compounds, for example sulfuric acid, perchloric acid, Phenylsulfonic acid, tosic acid, naphthene sulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, Tetrafluoroboric acid, phosphofluoric acid etc. for use.Consider that from catalytic effect, price and with reactant intermiscibility several respects the preferred tosic acid of the present invention is a catalyzer.
The consumption of acid catalyst has substantial connection with etherificate parent and the solvent system selected for use.For the inventive method, catalyst consumption is generally 0.02～0.2% of etherificate parent weight, and preferred usage quantity is between 0.05～0.1%, especially when acid catalyst is the Catalyzed by p-Toluenesulfonic Acid agent.The consumption of acid catalyst as is lower than 0.02% very little, and the speed of catalyst etherifying is too low, is difficult in the purpose that reaches full etherificate within 24 hours; The consumption of acid catalyst is too big, as greater than 0.2%, because etherate has high acidolysis active, the reaction etherate backward reaction that the later stage generated strengthens, often also be difficult to obtain the etherificate rate near 100% etherificate product, and give and determine that the termination reaction time brings very big difficulty.
In the methods of the invention, the solvent of etherification reaction is selected hydrochloric ether-cyclic ethers double solvents system for use, and this is that in other words, just the strength of acid to reaction system has shock absorption because ether compound or cyclic ether compounds all have the effect of inhaling proton.In addition, ether compound particularly cyclic ether compounds has the good solubility energy to phenolic compound and the etherifying reagent that the present invention proposes, so picture 1,4-dioxane, these cyclic ether compounds of tetrahydrofuran (THF) become the solvent that the inventive method must be used, and have also used the solvent as the tetrahydrofuran (THF) in some patent in the past.Single is effectively with cyclic ether compounds for the high acidolysis active etherate of composite part etherificate, still will obtain being bordering on 100% etherificate rate and can have certain difficulty.This be because, most of cyclic ether compounds is water miscible, water-retaining capacity is stronger, this etherification reaction for phenols and vinyl ethers etherifying reagent is totally unfavorable, even small amount of moisture also can obviously strengthen backward reaction and cause etherificate rate reduction.
In the methods of the invention, be preferably selected from the C of chloro as the hydrochloric ether of solvent
1-C
6The C of alkane and chloro
2-C
6Alkene is preferably selected from methylene dichloride, trieline, trichloromethane and zellon etc.The active etherate that etherification reaction generates is very easily dissolving in these hydrochloric ethers, and the repellency of these hydrochloric ethers is also very strong, and this has just suppressed backward reaction effectively, is convenient to obtain the etherificate rate and is bordering on 100% etherificate product.
Hydrochloric ether can be selected between 1: 1～10: 1 the weight ratio of cyclic ether compounds, and optimum amount is between 2: 1～5: 1.The ratio of double solvents gross weight and etherificate parent weight can be selected between 1: 1～10: 1, preferably selected between 2: 1～6: 1.Solvent load is too big, can slow down etherification reaction speed, solvent load very little, reaction solution viscosity is too big, both has been unfavorable for reacting homogeneous and has carried out, and influences the removal work of later stage acid catalyst again.
In the methods of the invention,, preferably under 10～20 ℃ temperature, carry out being reflected under 0～30 ℃ the temperature of etherificate parent etherificate with etherifying reagent.Temperature is too high, for example more than 30 ℃, near the boiling point of some hydrochloric ether and some etherifying reagent, should not adopt.Temperature is lower than 0 ℃, and etherification reaction speed is very slow, and the required etherificate time is oversize.Synthetic test shows, when reacting between 10～20 ℃, can guarantee certain etherificate speed, help obtaining the full etherificate product near 100% etherificate rate again, and the steam output of etherifying reagent is also minimum.
In the methods of the invention, the time of carrying out etherification reaction between etherificate parent and the etherifying reagent is depended on the acid catalyst and the double solvents system of use.When the etherification reaction of the inventive method carries out under 10～20 ℃, for most phenolic compounds, can reach or approaching full etherificate at 4～8 hours, indivedual phenols required times may be longer, even needed 24 hours could realize full etherificate.
Needed to follow the tracks of the etherificate rate (infrared spectroscopy) that detects every 2～4 hours in the etherification procedure, when general phenolic hydroxyl group absorb light density is reduced to 1/10th original left and right sides, can add the alkali neutralizing agent and remove acid catalyst.Because anhydrous sodium carbonate, magnesium oxide etc. can effectively be removed the moisture in the solvent system, if add this class neutralizing agent, along with stirring is carried out, moisture just is absorbed, etherification reaction carries out to the direction of thorough etherificate rapidly, after stirring 2 hours, the absorb light density of hydroxyl is zero (calculating by baseline method) substantially, and promptly etherification reaction is thoroughly finished.And then placed 8～24 hours, because acid catalyst does not exist, backward reaction can not carry out, the long-term placement is in order to react more thorough, gets moisture removal remaining in the system more thorough.
In the methods of the invention, the alkali neutralizing agent of use can preferably use anhydrous sodium carbonate and/or magnesium oxide for being selected from least a in anhydrous sodium carbonate, anhydrous sodium bicarbonate, magnesium oxide, calcium oxide, the γ-anhydrous alumina.The consumption of neutralizing agent depends on the consumption of acid catalyst, and usually, the consumption of neutralizing agent is at least 50 times of catalyst weight, especially when acid catalyst is tosic acid.
Stir suction, neutralizing acid catalyzer in the reaction system if adopt the alkali neutralizing agent joined, then leave standstill filtering method, the alkali neutralizing agent is preferably selected subparticle or Powdered for use, so that in improving and efficient; If adopt with the method for reaction solution by the acid removal column deacidification, then acid scavenger should adopt the particulate material of diameter between 0.1～0.2mm, reaction solution passes through the speed-controllable of acid removal column between 10～100ml/min, column length generally between 50～100cm, through acid removal column or the reaction solution after filtering under the reduced pressure of 10～50mmHg post, boil off unreacted etherifying reagent and most of solvent and obtain product in 60～70 ℃.
In the preferred embodiment of the inventive method, prepared formula (I) compound is each cited preferred compound of mutual-through type (I) compound above.
Formula of the present invention (I) compound has high acidolysis active at normal temperatures, can be used as the molten/chaotropic agent of resistance in imaging plate-making.
Embodiment
The listed embodiment of the present invention is not whole embodiment, but wherein representative a part of example.Embodiment 1～8th, through preferably, the synthesis example of comparatively practical monobasic phenols etherate.Pure phenol monomer of many operational analysis among the embodiment (Beijing Chemical Plant or Shanghai chemical reagent work produce) or industrial top grade product, manufacturer indicates in an embodiment in case of necessity.EVE and 2, the 3-dihydropyrane product of lark prestige chemical reagents corporation from external import.
The acid-decomposed activity of active etherate and hinder the measuring method of molten/short molten ability
Get full ether compound 2g of the present invention, photo-thermal produces acid source triazine D, and (1-is to methoxy styryl-3, two (trichloromethyl) triazines of 5-, Inst. of Applied chemistry, Beijing Normal Univ.) 0.2g, alkaline bright blue (dye processing plant, Tianjin) 0.2g, (Mw is 7000 to the BTB-25 resin, be the mixed phenol resol of M-and P-cresols with 6: 4 mol ratio, Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd.) 7.6g, ethylene glycol monoethyl ether 90g, dissolving is mixed with photosensitive solution.Be coated with on centrifugal coating machine, the control rotating speed makes the coating solid content reach about 2.0g/m
2Put into 110 ℃ dry 5 minutes of baking oven, sample is cut into 6～12 2 * 2cm after taking out cooling
2Little pressing.At first little pressing (that is, unexposed master) is put into 5% 9 water sodium silicate aqueous solutions, observe it and initially subtract the film loss of gloss time (second), as the measurement parameter of the molten ability of resistance.Little pressing being put into illumination again is 1mW/cm
2Black lamp (the output wavelength scope is 300-400nm, the maximum value wavelength is 365nm) exposure lamp under, naked exposure 100 seconds, 120 seconds, 150 seconds, 175 seconds, 200 seconds is put into respectively in 5% the sodium silicate aqueous solution again, soak and develop, observe the time (second) of cleaning.Exposing, (exposure was 120mJ/cm in 120 seconds
2) to clean the person in 30 seconds be high acidolysis active, exposure was cleaned the person to 150 seconds more than 120 seconds in 30 seconds be middle acid-decomposed activity, exposure second was cleaned a person to 200 seconds more than 150 seconds and is hanged down acid-decomposed activity 30 in, using value is still all arranged.This is corresponding PS version and the high, normal, basic sensitivity of heat-sensitive CTP plate and fixed acid-decomposed activity standard does not have the possibility of acidolysis even general etherate exposes yet more than 600 seconds.
Other gets a little pressing, and its clean time (second) is observed in naked exposure 200 seconds.To be decided to be short molten ability strong with cleaning the person below 20 seconds, and 20-40 is cleaned the person second, and to be decided to be short molten ability medium, with a little less than cleaning the person more than 40 seconds and being decided to be short molten ability.Little pressing initially subtracts the film loss of gloss time and minimum to clean the ratio of time big more, illustrate this hinder the resistance of molten chaotropic agent in plate-making molten/short molten ratio is big more, also closely related with the development latitude of plate.
Embodiment 1
Get industrial top grade product p-tert-butylphenol 15.0g (0.1mol), be dissolved in 15g 1, in the double solvents of 4-dioxane and 45.0g methylene dichloride, add the anhydrous tosic acid of 0.01g, after the stirring and dissolving, under 20 ℃, in 30 minutes, drip EVE 10.1g (0.14mol), stir after 2 hours standing and reacting at room temperature.Per 2 hours sampling and measuring infrared spectras are to 3300～3400cm
-1Place's phenolic hydroxyl group absorption peak absorb light density (calculating with baseline method) reduces to original 1/10th when following (being generally 8 hours), in 10 minutes, add Powdered anhydrous sodium carbonate 1.0g gradually, stirred 2 hours, left standstill then 8 hours, remove lixiviating neutralizing agent and paratoluenesulfonic acid sodium salt solid with the suction funnel suction filtration, filtrate changes in the matrass, 60～70 ℃ of control bath temperatures, under higher vacuum, boil off unreacted etherifying reagent and low boiling point solvent methylene dichloride and the overwhelming majority 1, the 4-dioxane.Obtain active etherate content and be 94% yellow thick liquid product P-1.
The composition structure of the active etherate that obtains is united affirmation by infrared spectroscopy and gas chromatography mass spectrometry assay method.Infrared spectra is mainly by 3350cm
-1The phenolic hydroxyl group absorption peak disappear and 1050cm
-1The absorption peak of left and right sides phenolic ether group occurs, and calculates the variation of optical density(OD) by baseline method, with the interior mark of being absorbed as of phenyl ring, calculates to such an extent that its etherificate transformation efficiency is bordering on 100%.Also observe the percentage of full ether compound simultaneously, and find out molecular ion peak, confirm that finally the structural formula of compound is shown below with the gas chromatography mass spectrometry assay method.
Embodiment 2
To the p-tert-butylphenol among the chloro-tert.-butylphenol replacement embodiment 1, the proportioning of other adding reagent, operation are fully with embodiment 1 with 18.5g (0.1mol).Obtain active etherate content and be 92% yellow thick liquid product P-2.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 3
With embodiment 1 identical method, just with 11.9g (0.14mol) 2, the 3-dihydropyrane replaces EVE.Obtain active etherate content and be 92% yellow thick liquid product P-3.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 4
Get 19.8g (0.1mol) 4-dihydroxy benaophenonel, be dissolved in 30g 1, in the double solvents of 4-dioxane and 60g methylene dichloride, add the anhydrous tosic acid of 0.02g, after the stirring and dissolving, under 20 ℃, in 30 minutes, drip the EVE of 10.1g (0.14mol), other are fully with embodiment 1.Obtain active etherate content and be 92% yellow thick liquid product P-4.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 5
Get 12.2g (0.1mol) 2,4-xylenol (lark waffle learn import product), the p-tert-butylphenol among the replacement embodiment 1, other are fully with embodiment 1, obtain active etherate content and be 95% yellow liquid product P-5.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 6
With 11.9g (0.14mol) 2, the 3-dihydropyrane replaces the EVE among the embodiment 5, and other are fully with embodiment 5, obtains active etherate content and be 94% yellow thick liquid product P-6.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 7
Get 17.8g (0.1mol) 2,6-dimethyl p-tert-butylphenol, be dissolved in the double solvents of 30g tetrahydrofuran (THF) and 30g methylene dichloride, add the anhydrous tosic acid of 0.01g, after the stirring and dissolving, under 20 ℃, in 30 minutes, drip the EVE of 10.1g (0.14mol), other are fully with embodiment 1.Obtain active etherate content and be 94% yellow thick liquid product P-6.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 8
Get 18g (0.1mol) propylparaben, be dissolved in 30g 1, in the double solvents of 4-dioxane and 50g trichloromethane, add the anhydrous tosic acid of 0.02g, dripped the EVE of 10.1g (0.14mol) after the stirring and dissolving in 30 minutes, other are fully with embodiment 1.Obtain active etherate content and be 90% yellow thick liquid product P-8.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Comparative Examples 1
Get 9.4g (0.1mol) phenol, replace the p-tert-butylphenol among the embodiment 1, other are fully with embodiment 1.Obtain active etherate content and be 95% faint yellow thick liquid product C P-1.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Comparative Examples 2
Get 22g (0.1mol) 2,6 ditertiary butyl p cresol, replace the p-tert-butylphenol among the embodiment 1, other are fully with embodiment 1.Obtain active etherate content and be 90% deep yellow thick liquid product C P-2.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Molten, the short dissolubility of the acid-decomposed activity of the active etherate that related parameter and mensuration are arranged of used etherificate parent monohydric phenol compound and full etherificate product and resistance can be listed in table 1 in embodiment 1～8 and Comparative Examples 1 and 2.
Embodiment 9～16 is the synthesis example of bisphenols high acidolysis active etherate, and embodiment 17 is the synthesis example of polyphenol high acidolysis active etherate.Analytical reagent is Beijing Chemical Plant and Shanghai chemical reagent work product, and industrial goods are selected industrial first grade for use, and external reagent indicates in an embodiment.
Embodiment 9
Get industrial first grade dihydroxyphenyl propane 22.8g (0.1mol), be dissolved in 20g analytical pure 1, in the double solvents of 4-dioxane and 40g methylene dichloride, add the anhydrous tosic acid of 0.01g, after the stirring and dissolving, in in 20 minutes, dripping EVE 20.2g (0.28mol) under the room temperature, stir sealing and standing reaction at room temperature after 2 hours.Per 2 hours sampling and measuring infrared spectras, reduce to original 1/10th when following (being generally 4 hours) to phenolic hydroxyl group absorption peak absorb light density, add magnesium oxide powder 1.0g, stirred 2 hours, left standstill then 8 hours, remove solid residue (magnesium oxide and tosic acid magnesium) with the suction funnel suction filtration, filtrate changes in the matrass, under the reduced pressure of 10～50mmHg post, reaction solution is heated to 60 ℃, unreacted etherifying reagent and the low boiling point solvent methylene dichloride and the overwhelming majority 1,4-dioxane are removed in distillation.Obtain active etherate content and be 94% faint yellow thick liquid product P-9.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 10
With 23.8g (0.28mol) 2, the 3-dihydropyrane replaces the 20.2g EVE among the embodiment 9, replace methylene dichloride among the embodiment 9 with the equivalent trieline, other are with embodiment 9, obtain active etherate content and be 92% faint yellow thick liquid product P-10.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 11
With the dihydroxyphenyl propane among 20.0g (0.1mol) the bis-phenol M replacement embodiment 10, other are fully with embodiment 10.Obtain active etherate content and be 92% yellow thick liquid product P-11.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 12
With the dihydroxyphenyl propane among 21.8g (0.1mol) the bisphenol S replacement embodiment 10, other are fully with embodiment 10.Obtain active etherate content and be 94% deep yellow thick liquid product P-12.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 13
With 25g (0.1mol) 4,4 '-dihydroxy-diphenyl sulfone replaces the dihydroxyphenyl propane among the embodiment 9, and other are fully with embodiment 9.Obtain active etherate content and be 92% yellow thick liquid product P-13.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 14
With 21.4g (0.1mol) 4,4 '-dihydroxy benaophenonel (Japanese Northeast chemical products) replaces the dihydroxyphenyl propane among the embodiment 9, with 1 among the tetrahydrofuran (THF) replacement embodiment 9 of equivalent, and the 4-dioxane, other are fully with embodiment 9.Obtain active etherate content and be 94% faint yellow thick liquid product P-14.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 15
With 22.8g (0.1mol) 3,3 '-dimethyl bis-phenol M (sky, Weihai becomes chemical industry company limited product) replaces the dihydroxyphenyl propane among the embodiment 9, and anhydrous tosic acid adds 0.015g, and other are fully with embodiment 9.Obtain active etherate content and be 93% deep yellow thick liquid product P-15.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 16
With 26.9g (0.1mol) 3,3 '-dichloro bis-phenol M (sky, Weihai becomes chemical industry company limited product) replaces the dihydroxyphenyl propane among the embodiment 9, with the solvent among 30g tetrahydrofuran (THF) and the 90g methylene dichloride replacement embodiment 9, anhydrous tosic acid adds 0.015g, and other are fully with embodiment 9.Obtain active etherate content and be 98% pale brown look thick liquid product P-16.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Embodiment 17
With 35.2g (0.1mol) 2,6-dihydroxymethyl p-cresol two Resorcinols (sky, Weihai becomes chemical industry company limited product) that contract replace dihydroxyphenyl propane among the embodiment 9, with 60g 1,4-dioxane and 180g methylene dichloride replace the solvent among the embodiment 9, anhydrous tosic acid adds 0.01g, the EVE add-on is 43.4g (0.6mol), and other are fully with embodiment 9.Obtain active etherate content and be 90% pale brown look utmost point thick liquid product P-17.The active etherate that obtains with the same composition structural confirmation method of embodiment 1, is determined that its structural formula is as follows:
Comparative Examples 3
Do not add the Catalyzed by p-Toluenesulfonic Acid agent, corresponding neutralization procedure also saves, and other are fully with embodiment 9.Obtain product C P-3, with the composition structural confirmation method of embodiment 1, determine that its component mainly is unreacted dihydroxyphenyl propane, the etherificate rate is less than 10%.
Comparative Examples 4
With the double solvents among the 60g tetrahydrofuran (THF) replacement embodiment 9, other are fully with embodiment 9.Obtain product C P-4, with the composition structural confirmation method of embodiment 1, determine that its component mainly is single etherate of dihydroxyphenyl propane, the etherificate rate is approximately 60%.
Comparative Examples 5
With the dihydroxyphenyl propane among 23.0g (being about as much as dihydric phenol 0.1mol) the BTB-26 resin replacement embodiment 9, as etherifying reagent, other are fully with embodiment 9 with 10.1g (0.14mol) EVE, but last the need at 80 ℃ of abundant pressure reducing and steaming solvents.Obtain product C P-5, with the composition structural confirmation method of embodiment 1, determine that its component mainly is the part etherate of line style phenol resins, the etherificate rate is approximately 50%.
The BTB-26 resin is the film forming lacquer resins that Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. produces, be phenol, p-cresol, meta-cresol terpolymer resin, weight-average molecular weight about 3400, number-average molecular weight 1100, repeating unit is about 10, molecular weight distributing index 3.1.
Molten, the short dissolubility of the acid-decomposed activity of the active etherate of the correlation parameter of used etherificate parent and etherificate product and mensuration and resistance can be listed in table 2 in embodiment 9～17 and the Comparative Examples 3～5.
Invention effect and conclusion
From monohydric phenol active etherate P-1～P-8 and bisphenols active etherate P-9～P-17 and polyphenol (low molecule phenol resins) active etherate P-18 related parameter and performance arranged, and can clearly obtain as drawing a conclusion with the comparing result of Comparative Examples 1～5 monohydric phenol, bisphenols and high molecular phenol resins active etherate:
1. its phenol monomer molecule amount of monohydric phenol active etherate with practical value should be between 120～180, the M/A value is between 8.0～11.0, full ether compound molecular weight is between 190～260, and ether equivalent (E) is between 97～135, and the ratio of ether equivalent and M/A value is between 11.5～14.5.Active etherate for bisphenol compound, its phenolic compound molecular weight of etherate should be between 200～300 preferably for most with practical value or imaging performances, the M/A value is between 5.6～8, little more many than the monomeric M/A value of monohydric phenol, the molecular weight of full ether compound is between 344～444, the ether equivalent is between 90～110, as doing etherifying reagent with EVE, the ratio of ether equivalent and M/A value is between 12.6～14.6, if consider that the more weak phenol of the molten ability of part resistance is with 2, the 3-dihydropyrane is done etherifying reagent, and this value should be between 12.6～16.5, and it is big that the numerical value of this odds ratio monohydric phenol is wanted.
2. according to the rule of summing up in the past, the acid-decomposed activity of active etherate (sensitivity), the molten ability of resistance and short molten ability imaging performances such as (development latitudes) and etherificate parent phenolic compound and M/A value have substantial connection, molecular weight is more little, the M/A value is more little, and caustic solubility is good more.Because the degradation production after the active etherate scanning is exactly a phenolic compound, the M/A value can be used as the scale of short molten ability.But the M/A value can not be too little, is easy to subtract the film loss of gloss too for a short time, is difficult to obtain image.The molecular weight of active etherate is big more, and the ether equivalent of full ether compound is big more, and the molten ability of its resistance is strong more, so the ether equivalent can think to hinder the molten/size of short molten ratio and the size of development latitude with the ratio size of M/A value.From the data of conclusion 1 as can be seen, the molecular weight of bisphenol compound is big, and all the respective value than monohydric phenol is big for the ratio of ether equivalent and ether equivalent and M/A value, so they have molten, the short molten ability of better resistance, the latitude of also both better having developed.What is interesting is that no matter be monohydric phenol active etherate or bisphenols active etherate, all in a very little scope, this is the thing of a regularity seemingly for the ether equivalent of etherate wherein the most with practical value and the ratio of M/A value.Imaging test has confirmed above-mentioned viewpoint fully.
3. from embodiment 1～17 and Comparative Examples 3 as can be seen, except the polyphenolic substance with resorcinol derived can use no or little the Catalyzed by p-Toluenesulfonic Acid agent, nearly all monohydric phenol and bisphenol compound all need to add the acid catalyst of specified amount when synthesizing etherate, just might carry out etherification reaction smoothly and might obtain full ether compound.And can learn from the data of Comparative Examples 4 gained etherates, even used the acid catalyst of appropriate amount, the etherificate solvent does not adopt double solvents system of the present invention, as adopting the single solvent in the previous patent, though can carry out etherification reaction, etherification reaction is not thorough.If single with 1, the 4-dioxane also can run into same situation, particularly use the technical grade water content bigger 1, the 4-dioxane often is difficult to obtain the etherate of desired etherificate rate.So using the catalyst for etherification and the double solvents system of the present invention of specified amount also is one of key character of the present invention.
4. can know from the comparison of Comparative Examples 5 and embodiment 1～17 and find out, use the higher resol of molecular weight to do the etherificate parent, though be easy to obtain near solid etherificate product, beneficial to anti-dry grinding property of rete and raising pressrun, but with the present invention particularly bisphenol compound compare, following weak point is arranged:
(1) is not easy to obtain 100% etherificate rate;
(2) though the etherificate rate about 50%, the imaging sensitivity is also lower, the development latitude is poor, it is dirty easily to keep on file.So lower molecular weight high acidolysis active phenolic ether, particularly bisphenols etherate provided by the invention are principal characters of the present invention.
Claims (11)
1. general formula (I) compound
X is in the formula
R
1Be
R
2Be H, C independently of one another
1-C
4Alkyl or-OR
4, be preferably hydrogen, methyl or-OR
4,
R
3Be H, C independently of one another
1-C
4Alkyl or halogen are preferably hydrogen, methyl, chlorine or bromine,
R
5Be H, C independently of one another
1-C
4Alkyl or halogen are preferably hydrogen, methyl or bromine,
R
4Be C
1-C
6Alkyl-O-CH (CH
3)-or
2. as the desired compound of claim 1, it is to be selected from following compound:
3. synthetic method as the desired general formula of claim 1 (I) compound is characterized in that:
Work as R
1For-CH
3,-CH
2Cl ,-Ph or-OC
3H
7The time, make following formula (II) compound as the etherificate parent
Perhaps, work as R
1For
The time, make following formula as the etherificate parent
(III) compound
Be selected from vinyl C as etherifying reagent
1-C
6Alkyl oxide and 2, the compound of 3-dihydropyrane is reacting in the double solvents at hydrochloric ether-cyclic ether compounds in the presence of the acid catalyst, wherein variable X and R
1-R
5Have implication separately as providing in the claim 1, and formula (II) and (III) molecular weight of compound between 100～400.
4. as the desired method of claim 3, its Chinese style (II) and (III) compound be selected from following compound: 2,4-xylenol, 3,4-xylenol, p-tert-butylphenol, to chloro-tert.-butylphenol, to benzoyl phenol, 2,6-dimethyl p-tert-butylphenol, propylparaben and to thiophenyl phenol; 4,4 '-dioxydiphenyl methane, 4,4 '-dihydroxy benaophenonel, dihydroxyphenyl propane, 4,4 '-dihydroxyl phenylbenzene sulphur, 4,4 '-dihydroxy-diphenyl sulfone, 3,3 '-dimethyl bis-phenol M, 3,3 '-dichloro bis-phenol M; And 2,6-dihydroxymethyl p-cresol two Resorcinol condensess that contract.
5. as claim 3 or 4 desired methods, wherein etherifying reagent is selected from following compound: EVE, vinyl propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl-, vinyl sec-butyl ether, vinyl tertbutyl ether and 2, the 3-dihydropyrane, be preferably selected from EVE and 2, the 3-dihydropyrane.
6. as each desired method among the claim 3-5, wherein the consumption of etherifying reagent is 1.2～1.5 times of etherificate parent phenolic hydroxyl group mole number in mole.
7. as each desired method among the claim 3-6, wherein said acid catalyst is selected from following compound: sulfuric acid, Phenylsulfonic acid, tosic acid and trifluoromethanesulfonic acid, preferred tosic acid.
8. as each desired method among the claim 3-7, the consumption of wherein said acid catalyst is 0.02～0.2%, preferred 0.05～0.1% of an etherificate parent weight.
9. as each desired method among the claim 3-8, wherein said hydrochloric ether is selected from the C of chloro
1-C
6The C of alkane and chloro
2-C
6Alkene is preferably selected from methylene dichloride, trieline, trichloromethane and zellon; And described cyclic ether compounds is selected from 1,4-dioxane and tetrahydrofuran (THF), wherein the weight ratio of hydrochloric ether and cyclic ether compounds is 1: 1～10: 1, and the preferred hydrochloric ether-gross weight of cyclic ether compounds double solvents and the weight ratio of etherificate parent are 8: 1～2: 1.
10. as each desired method among the claim 3-9, wherein in the reaction mixture that etherification reaction obtains, add the alkali neutralizing agent, preferred this alkali neutralizing agent is selected from following compound: anhydrous sodium carbonate, anhydrous sodium bicarbonate, magnesium oxide and calcium oxide, preferably the consumption of this alkali neutralizing agent is at least 50 times of acid catalyst consumption.
11. as each desired method among the claim 3-10, wherein Zhi Bei formula (I) compound is to be selected from following compound:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105330A (en) * | 2021-04-15 | 2021-07-13 | 北京科华微电子材料有限公司 | Phenolic compound, preparation method and application thereof, and photoresist |
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| US3775113A (en) * | 1972-02-09 | 1973-11-27 | Minnesota Mining & Mfg | Positive image transfer |
| JPH10186663A (en) * | 1996-12-26 | 1998-07-14 | Sumitomo Chem Co Ltd | Positive photoresist composition |
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