CN101693758A - Synthesis of carboxylic phenol resin active ester and etherate - Google Patents
Synthesis of carboxylic phenol resin active ester and etherate Download PDFInfo
- Publication number
- CN101693758A CN101693758A CN200910236587A CN200910236587A CN101693758A CN 101693758 A CN101693758 A CN 101693758A CN 200910236587 A CN200910236587 A CN 200910236587A CN 200910236587 A CN200910236587 A CN 200910236587A CN 101693758 A CN101693758 A CN 101693758A
- Authority
- CN
- China
- Prior art keywords
- etherate
- phenolic resin
- active ester
- resin active
- carboxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a synthesis of carboxylic phenol resin active ester and etherate in the technical field of functional high polymer material preparation. The synthesizing method is got through the reaction of carboxylic phenol resin, etherified reagent and catalyst. The synthesized carboxylic phenol resin active ester and etherate have higher light sensitivity, and can be used to the traditional PS edition, thermal sensitive CTP edition, photosensitive resist, electron beam resists or chemical amplitude resists and the like. Compared with the prior art, the synthesis does not need esterification in advance, carboxylic phenol resin is directly etherified under the function of catalyst, and the invention has high etherified ratio, excellent comprehensive property, excellent stability and convenient storage, and the product yield is solid.
Description
Technical field
The invention belongs to field of polymer material preparing technology, particularly carboxyl phenolic resin active ester and etherate is synthetic.
Background technology
In 3M company nineteen ninety invention disclosed patent (USP618212 (1990)), they obtain the diphenyl acetic acid ester with the compound addition of diphenyl acetic acid and chloromethyl methyl ether, EVE, dihydropyrane, dihydrofuran isoreactivity alkene.This class ester mixes with certain proportion with acidogenic agent, linear phenolic resin and additive, with appropriate solvent dissolve, film, drying, the resist coating that obtains partly produces protonic acid in the uv-exposure post-exposure, the diphenyl acetic acid active ester is decomposed, thereby the available bases water development obtains image, is used for making positive PS printing plate or positive photoresist.Yet the invention of 3M company has two big serious problems: 1. this compound stability can be poor, deposits at normal temperatures, particularly runs into light and moisture and oneself decompose with regard to very fast, preserves difficulty.2. this compound is the low liquid of a kind of viscosity pole, is added in film strength decline in the CTP version photosensitive composition, has a strong impact on pressrun.Its anti-printing ink solvent ability is also very poor in addition: be used for the photo-resist thermotolerance and antiacid erosion is also very poor.
In the prior art, application number is to disclose a kind of high acidolysis active ester ether compound or ether compound and synthetic method thereof based on linear phenol resins in the Chinese patent of CN1459463.The high acidolysis active ester ether compound or the ether compound based on linear phenol resins of this invention utilize poly(4-hydroxystyrene) (PHS), linear phenolic resin and other linear polymeric that contains phenolic group to carry out partial esterification with esterifying reagent earlier, then further with etherifying reagent in solvent, in acid catalysis or do not have that to carry out etherificate under the acid catalyzed condition synthetic.The deficiency of this invention is at first to need esterification, carries out etherificate again.Compound is under the effect of acidogenic agent, and generally just the part of etherificate is dissociated, and the part of esterification is not dissociated basically, and it is little to make that the exposure front and back change, thereby hinders molten short molten DeGrain.
Application number is the synthetic side who discloses a kind of ester ether compound of high acidolysis active in the Chinese patent of CN 1347869A, this invention is to utilize benzil acid (2,2-phenylbenzene oxyacetic acid) with various phenolic compound reaction, at least also residual more than one active site on the phenyl ring in these phenolic compounds, make catalyzer (to drop into solid material weight) with the tosic acid of 0.1%-2%, with toluene, benzene-like compounds such as dimethylbenzene are solvent, under reflux temperature, reflux water-dividing to aquifer yield arrives the regulation mole number, synthesized the affixture of a series of benzil acid and phenols, perhaps further dehydration generates lactone compound.Utilize these affixtures or lactonize thing and EVE, dihydropyrane, dihydrofuran, pyrrolin, and alkene ether compound such as chloromethyl methyl ether, at normal temperature or below the 70 ' C, carry out the addition etherification reaction, can generate ester, the ether compound of a series of novel high acidolysis actives.But the etherificate parent in this technology is single compound, make its etherificate ester, ether compound basically all be dope, be inconvenient to preserve and use.This compound is added in film strength decline in the CTP version photosensitive composition, influences the space of a whole page of pressrun and plate.
Summary of the invention
The invention provides the synthetic of a kind of carboxyl phenolic resin active ester and etherate, it is made up of in the following general formula one or more and forms:
Wherein x is 0-2, and n is that 2-15 is, p is 0-13, R
1Be the alkyl of H or C1-C4, R
2Alkyl for C1-C4.
Synthetic method of the present invention is as follows:
In the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer, add resin, catalyzer and solvent, drip etherifying reagent with constant pressure funnel, per 100 parts by volume solvents add 5-20 parts by weight resin, 0.2-1.5 weight part catalyzer and 60-150 parts by volume etherifying reagent, after being added dropwise to complete, room temperature reaction 3-20h, after the washing, vacuum-drying, obtain yellow solid, i.e. carboxyl phenolic resin active ester and etherate; The pass of described weight part and parts by volume is g/ml or kg/l.
Described resin is a carboxylic phenolic resin; Etherifying reagent is ethyl vinyl ether, VINYL ISOBUTYL ETHER, vinyl n-butyl ether or dihydropyrane, preferred vinyl ether or VINYL ISOBUTYL ETHER; Catalyzer is acetonyl triphenyl bromide phosphine, organic or inorganic weak acid, comprises phosphoric acid, trichoroacetic acid(TCA), tosic acid, thionamic acid, preferred acetonyl triphenyl bromide phosphine or thionamic acid; Solvent is ordinary organic solvents ether, tetrahydrofuran (THF) or the organic solvent 1 that contains halogen, 2-ethylene dichloride, methylene dichloride, trichloromethane, tetrachloromethane, 1,2-dichloroethene, preferred methylene dichloride, 1,2-dichloroethene.
Synthetic carboxyl phenolic resin active ester of the present invention and etherate have very high photolytic activity, can be used for aspects such as traditional PS version, heat-sensitive CTP plate and photo-resist, electron sensitive resist or chemically amplified photo resist agent, compared with prior art, the present invention has following advantage:
1) do not need esterification in advance, but carboxylic phenolic resin direct etherificate under catalyst action;
2) the active ester etherate is easy to deprotection under action of protonic, makes that its exposure front and back solubility contrast in alkaline-based developer is very big, thereby improves the development and the imaging performance of plate;
3) the etherificate rate height of the active etherate that obtains of used new catalyst, thereby make exposure region and the non-exposed area solvability in alkaline-based developer produce very big-difference, over-all properties is better;
4) product is a solid, and good stability, preservation are conveniently.
Below in conjunction with embodiment, the invention will be further described, rather than limit the scope of the invention.
Embodiment
Embodiment 1:
Adding the 13g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-10, the 100mL ether, 1.00g phosphoric acid, drip the 100ml ethyl vinyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 6h, after the washing, vacuum-drying obtains the 12.6g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 2:
Adding the 5g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-10,100mL 1, the 2-ethylene dichloride, 0.5g acetonyl triphenyl bromide phosphine drips the 60ml ethyl vinyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 6h, after the washing, vacuum-drying, obtain the 5.1g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 3:
Adding the 6g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-10, the 100mL methylene dichloride, 0.2g acetonyl triphenyl bromide phosphine, drip the 70ml ethyl vinyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 3h, after the washing, vacuum-drying obtains the 6.3g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 4:
Adding the 8g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-10, the 100mL trichloromethane, 0.8g acetonyl triphenyl bromide phosphine, drip the 80ml ethyl vinyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 5h, after the washing, vacuum-drying obtains the 8.2g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 5:
Adding the 12g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-10,100mL 1, the 2-Ethylene Dichloride, the 1.00g trichoroacetic acid(TCA) drips the 120ml ethyl vinyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 8h, after the washing, vacuum-drying, obtain the 13.7g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 6:
Adding the 15g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-10,100mL 1, the 2-Ethylene Dichloride, the 1.2g tosic acid drips the 100ml ethyl vinyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 10h, after the washing, vacuum-drying, obtain the 17.1g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 7:
Adding the 10.4g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-20,100mL 1, the 2-Ethylene Dichloride, the 1.5g thionamic acid drips the 150ml ethyl vinyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 12h, after the washing, vacuum-drying, obtain the 15.1g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 8:
Adding the 15g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-20,100mL 1, the 2-Ethylene Dichloride, 1.4g acetonyl triphenyl bromide phosphine drips the 140ml dihydropyrane with constant pressure funnel, after being added dropwise to complete, room temperature reaction 14h, after the washing, vacuum-drying, obtain the 22.8g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 9:
Adding the 18g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-20,100mL 1, the 2-Ethylene Dichloride, the 1.3g thionamic acid drips the 120ml dihydropyrane with constant pressure funnel, after being added dropwise to complete, room temperature reaction 16h, after the washing, vacuum-drying, obtain the 31.0g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 10:
Adding the 12g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-50,100mL 1, the 2-Ethylene Dichloride, 1.00g acetonyl triphenyl bromide phosphine drips the 100ml VINYL ISOBUTYL ETHER with constant pressure funnel, after being added dropwise to complete, room temperature reaction 18h, after the washing, vacuum-drying, obtain the 23.2g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 11:
Adding the 10.5g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-50, the 100mL methylene dichloride, 1.2g acetonyl triphenyl bromide phosphine, drip the 80ml VINYL ISOBUTYL ETHER with constant pressure funnel, after being added dropwise to complete, room temperature reaction 20h, after the washing, vacuum-drying obtains the 20.7g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 12:
Adding the 8g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-50,100mL 1, the 2-ethylene dichloride, the 0.5g thionamic acid drips the 120ml VINYL ISOBUTYL ETHER with constant pressure funnel, after being added dropwise to complete, room temperature reaction 12h, after the washing, vacuum-drying, obtain the 16.1g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 13:
Adding the 10g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-50,100mL 1, the 2-ethylene dichloride, 0.9g acetonyl triphenyl bromide phosphine drips 120ml vinyl n-butyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 16h, after the washing, vacuum-drying, obtain the 20.3g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 14:
Adding the 10.5g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-70,100mL 1, the 2-ethylene dichloride, the 0.5g thionamic acid drips 100ml vinyl n-butyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 10h, after the washing, vacuum-drying, obtain the 23.1g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 15:
Adding the 16g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-70,100mL 1, the 2-Ethylene Dichloride, the 0.8g tosic acid drips 150ml vinyl n-butyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 12h, after the washing, vacuum-drying, obtain the 36.8g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Embodiment 16:
Adding the 6g code in the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer is the carboxylic phenolic resin of DF-70,100mL 1, the 2-Ethylene Dichloride, the 0.4g thionamic acid drips 90ml vinyl n-butyl ether with constant pressure funnel, after being added dropwise to complete, room temperature reaction 12h, after the washing, vacuum-drying, obtain the 13.0g yellow solid, i.e. carboxyl phenolic resin active ester and etherate.
Claims (9)
1. carboxyl phenolic resin active ester and etherate is characterized in that, it is made up of in the following general formula one or more and forms:
Wherein x is 0-2, and n is that 2-15 is, p is 0-13, R
1Be the alkyl of H or C1-C4, R
2Alkyl for C1-C4.
2. carboxyl phenolic resin active ester and etherate is synthetic, it is characterized in that its concrete preparation process is as follows:
In the four-hole bottle that has agitator, prolong, constant pressure funnel and thermometer, add resin, catalyzer and solvent, drip etherifying reagent with constant pressure funnel, per 100 parts by volume solvents add 5-20 parts by weight resin, 0.2-1.5 weight part catalyzer and 60-150 parts by volume etherifying reagent, after being added dropwise to complete, room temperature reaction 3-20h, after the washing, vacuum-drying, obtain yellow solid, i.e. carboxyl phenolic resin active ester and etherate; The pass of described weight part and parts by volume is g/ml or kg/l.
3. synthesizing of a kind of carboxyl phenolic resin active ester according to claim 2 and etherate, it is characterized in that described resin is a carboxylic phenolic resin.
4. synthesizing of a kind of carboxyl phenolic resin active ester according to claim 2 and etherate, it is characterized in that described etherifying reagent is ethyl vinyl ether, VINYL ISOBUTYL ETHER, vinyl n-butyl ether or dihydropyrane.
5. synthesizing of a kind of carboxyl phenolic resin active ester according to claim 2 and etherate, it is characterized in that, described catalyzer is acetonyl triphenyl bromide phosphine, organic or inorganic weak acid, comprises phosphoric acid, trichoroacetic acid(TCA), tosic acid, thionamic acid.
6. synthesizing of a kind of carboxyl phenolic resin active ester according to claim 2 and etherate, it is characterized in that, described solvent is ordinary organic solvents ether, tetrahydrofuran (THF), the organic solvent 1 that perhaps contains halogen, 2-ethylene dichloride, methylene dichloride, trichloromethane, tetrachloromethane, 1,2-dichloroethene.
7. synthesizing of a kind of carboxyl phenolic resin active ester according to claim 4 and etherate, it is characterized in that described etherifying reagent preferred vinyl ether or VINYL ISOBUTYL ETHER.
8. synthesizing of a kind of carboxyl phenolic resin active ester according to claim 5 and etherate, it is characterized in that described catalyzer preferred acetonyl triphenyl bromide phosphine or thionamic acid.
9. synthesizing of a kind of carboxyl phenolic resin active ester according to claim 6 and etherate, it is characterized in that the preferred methylene dichloride of described solvent, 1,2-dichloroethene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910236587A CN101693758A (en) | 2009-10-30 | 2009-10-30 | Synthesis of carboxylic phenol resin active ester and etherate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910236587A CN101693758A (en) | 2009-10-30 | 2009-10-30 | Synthesis of carboxylic phenol resin active ester and etherate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101693758A true CN101693758A (en) | 2010-04-14 |
Family
ID=42092763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910236587A Pending CN101693758A (en) | 2009-10-30 | 2009-10-30 | Synthesis of carboxylic phenol resin active ester and etherate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101693758A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018133214A1 (en) * | 2017-01-20 | 2018-07-26 | 中国科学院化学研究所 | Modified phenol-aldehyde resin and synthesis method therefor, hydrophilic plate for printing and use thereof, and printing plate |
| CN108329445A (en) * | 2017-01-20 | 2018-07-27 | 中国科学院化学研究所 | A kind of phenolic resin esterification benzene sulfonate and its synthetic method, printing hydrophilic version and application and galley |
| CN111154053A (en) * | 2020-01-06 | 2020-05-15 | 苏州瑞红电子化学品有限公司 | High-heat-resistance carboxyl phenolic resin and synthetic method thereof |
| CN111176073A (en) * | 2020-01-06 | 2020-05-19 | 苏州瑞红电子化学品有限公司 | Thick film photoresist composition containing high-heat-resistance carboxyl phenolic resin |
-
2009
- 2009-10-30 CN CN200910236587A patent/CN101693758A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018133214A1 (en) * | 2017-01-20 | 2018-07-26 | 中国科学院化学研究所 | Modified phenol-aldehyde resin and synthesis method therefor, hydrophilic plate for printing and use thereof, and printing plate |
| CN108329445A (en) * | 2017-01-20 | 2018-07-27 | 中国科学院化学研究所 | A kind of phenolic resin esterification benzene sulfonate and its synthetic method, printing hydrophilic version and application and galley |
| CN108329445B (en) * | 2017-01-20 | 2019-05-03 | 中国科学院化学研究所 | A kind of phenolic resin esterification benzene sulfonate and its synthetic method, printing hydrophilic version and application and galley |
| CN111154053A (en) * | 2020-01-06 | 2020-05-15 | 苏州瑞红电子化学品有限公司 | High-heat-resistance carboxyl phenolic resin and synthetic method thereof |
| CN111176073A (en) * | 2020-01-06 | 2020-05-19 | 苏州瑞红电子化学品有限公司 | Thick film photoresist composition containing high-heat-resistance carboxyl phenolic resin |
| CN111176073B (en) * | 2020-01-06 | 2023-11-07 | 苏州瑞红电子化学品有限公司 | Thick film photoresist composition containing high heat resistance carboxyl phenolic resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101693758A (en) | Synthesis of carboxylic phenol resin active ester and etherate | |
| CN105399943A (en) | Preparation method and application of anti-soil polymer | |
| CN104557552A (en) | Starlike tetraphenylethylene derivative molecular glass, positive photoresist, positive photoresist coating and application thereof | |
| CN107868243A (en) | The preparation method of the phosphorous acid water reducer of one derived from amino acid | |
| KR20110131904A (en) | Photoacid generator, mathod for manufacturing the same and resist composition comprising the same | |
| KR20120080163A (en) | Cyclic compound, manufacturing method therefor, radiation-sensitive composition, and method for forming a resist pattern | |
| CN101696266B (en) | Active etherate of pyrogallol and divinyl benzene polycondensate resin and synthesizing method thereof | |
| WO2020110793A1 (en) | Photosensitive resin composition, method for producing cured product of fluororesin, fluororesin, fluororesin film, bank and display element | |
| Pan et al. | A mild and practical method for deprotection of aryl methyl/benzyl/allyl ethers with HPPh 2 and t BuOK | |
| CN101696257B (en) | Active etherate of pyrogallol acetonide resin and synthesizing method thereof | |
| CN102153701B (en) | Catalyst for ternary polymerization of norbornene, acrylate and cyclohexene and preparation method thereof and ternary polymerization method | |
| JPS61256347A (en) | Alkali-soluble siloxane polymer | |
| CN110947423B (en) | Catalyst for synthesizing propylene glycol ether and preparation method thereof | |
| CN102250131B (en) | Dialkoxy aluminum complexe coordinated by beta-diketiminato ligand, its preparation method and application in epsilon-caprolactone ring-opening polymerisation | |
| CN107266319B (en) | Dendritic polyphenyl substituted adamantane derivative monomolecular resin, positive photoresist composition and negative photoresist composition | |
| CN105061164A (en) | Method for preparing triarylmethane compounds by utilizing catalysis of [ChCl][ZnCl2]2 | |
| CN1174974C (en) | Synthesis of ester ether compound with high acidolysis activity | |
| Hosoi et al. | Synthesis of stable acid amplifiers that produce strong highly-fluorinated polymer-bound acid | |
| JP2009196904A (en) | Cyclic compound and its production method | |
| Li et al. | Novel one-component molecular glass photoresist based on cyclotriphosphazene containing t-butyloxy carbonyl group for i-line lithography | |
| CN105363492B (en) | A kind of catalyst for acid anhydrides method synthesis of acetic acid ester and prepare the method for acetic acid esters using it | |
| Liu et al. | Single-component chemically amplified i-line molecular glass photoresist based on calix [4] resorcinarenes | |
| Tsuchimura et al. | Novel acid amplifier generating disulfonimide as superacid | |
| CN101104679A (en) | Aromatic diacid ester acetal polymer, synthetic method and use thereof | |
| CN101851222A (en) | Synthetic method of 2-amido-3-nitrile-4-nitromethyl-4H-chromene and derivative thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100414 |