CN101139427A - Preparation and use of water-soluble phenol resin containing tertiary amine oxide lateral group - Google Patents
Preparation and use of water-soluble phenol resin containing tertiary amine oxide lateral group Download PDFInfo
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- CN101139427A CN101139427A CNA2007101760793A CN200710176079A CN101139427A CN 101139427 A CN101139427 A CN 101139427A CN A2007101760793 A CNA2007101760793 A CN A2007101760793A CN 200710176079 A CN200710176079 A CN 200710176079A CN 101139427 A CN101139427 A CN 101139427A
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Abstract
The present invention relates to the preparation and the application of water-soluble phenolic resin with side-tertiary amine oxide. The water-soluble phenolic resin with side-tertiary amine oxide is of the following chemical structure: in which: A is methylene, -CH<SUB>2</SUB>COO-,-CH<SUB>2</SUB>CH<SUB>2</SUB>COO-,-C<SUB>6</SUB>H<SUB>5</SUB>COO-; B is methyl, ethyl; C is methyl, ethyl. The number-average molecular weight is 900 to 10000, with the epoxy value between 0.20 mol per 100 grams and 0.55 mol per 100 grams. The side chain of the present invention is of water-soluble phenolic resin with side-tertiary amine oxide, which is of the following characteristics: (1) easy preparation and good water-solubility; (2) the resin is non-ionic polymer, without halogen ions and metal ions; (3) as the axidized tertiary amine mass is relatively-stable when the temperature is under 140 DEG C, but is liable to decomposition when the temperature is above 150 DEG C (the decomposition product is of no gas), the water-soluble phenolic resin with side-tertiary amine oxide can be used as heat-sensitive materials;(4) Low toxicity.
Description
Technical field
The present invention relates to contain water soluble phenol resin and the preparation and the application of tertiary amine oxide side group.
Background technology
The epoxy group content height of epoxy phenolics, resin viscosity is big, and the cured article cross-linking density is big, has good thermostability, mechanical property, electrical insulating property, water tolerance and erosion resistance.Can be used for moulding processs such as lamination, mold pressing, winding, cast to make glass fibre reinforced plastic structure spare, electric elements etc., also can be used as tackiness agent, thermosensitive imaging system etc.
At present, along with the raising of people's environmental consciousness, the research of water soluble phenol resin obtains paying attention to.Epoxy phenolics is easy to carry out modification owing to have the higher epoxide group of reactive behavior, introduces various functional groups, gives the resol property.For example, by epoxide group and the substance reaction that contains hydrophilic radical, can introduce hydrophilic radical, the preparation water soluble phenol resin at the resol side chain.
People such as Xie Hongquan (Journal of Applied Polymer Science, 2004,91 (5): 2914-2922.) quaternary ammonium salt group is incorporated into the resol side chain, obtains water-soluble photosensitive resol, be expected to as environment-friendly type printed-wiring board (PWB) photocuring solder resist., because quaternary amine contains chlorion, the strong and stable performance of water-absorbent, unfavorable to the application of resin.People such as Gao Yu (polymer material science and engineering, 2004,20 (1): 65-67.) design preparation side chain contains the water soluble phenol resin of quaternary ammonium hydroxide group, but quaternary ammonium hydroxide is a highly basic, poor stability, corrodibility is strong, and practical value is little.In addition, the someone will be contained the monomer and the epoxy phenolics reaction of carboxyl and hydroxyl isopolarity group, and preparation contains the resol of carboxyl and hydroxyl, but these methods are for improving the water miscible limited in one's ability of resol.
Therefore the water soluble phenol resin that develop a kind of good water solubility, is easy to prepare, have sensitive characteristic and the feature of environmental protection and good stability just becomes this technical field and is badly in need of the technical barrier that will solve.
Summary of the invention
One of purpose of the present invention provides a kind of good water solubility, is easy to prepare, have the water soluble phenol resin of sensitive characteristic and the feature of environmental protection and good stability.
Above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of water soluble phenol resin, its chemical structure is as follows:
Wherein: A be methylene radical ,-CH
2COO-,-CH
2CH
2COO-,-C
6H
5COO-; B is methyl, ethyl; C is methyl, ethyl; Its number-average molecular weight is 900-10000, and oxirane value is between 0.20-0.55mol/100g.
Another object of the present invention provides a kind of preparation method of above-mentioned water soluble phenol resin.
Above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of preparation method who contains the water soluble phenol resin of tertiary amine oxide side group, step is as follows:
1. the organic acid that 10-55 part is contained the tertiary amine oxide group dissolves in the organic solvent of 10-100 part and generates corresponding solution (1);
2. 100 parts of epoxy phenolicss are dissolved in 70-200 part organic solvent and generate corresponding solution (2);
3. with solution (1) and solution (2),, obtain water soluble phenol resin solution at 50-100 ℃ of following stirring reaction 1-10 hour.
A kind of optimal technical scheme is characterized in that: the described organic acid that contains the tertiary amine oxide group means the organic compound with following chemical structure.
A kind of optimal technical scheme, it is characterized in that: the organic solvent in described step (1) and (2) is acetone, tetrahydrofuran (THF), dioxane, ethyl acetate, ethylene glycol monoemethyl ether, N-Methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc) and composition thereof.
The chemical structure of the epoxy phenolics of aforesaid method gained is as follows:
The molecular weight of epoxy phenolics (number average) is 900-10000, and oxirane value is between 0.20-0.55mol/100g.
In the method, it is as follows to contain the chemical reaction process of resol of tertiary amine oxide side group:
Above-mentioned purpose of the present invention can also reach by the following technical programs:
A kind of preparation method who contains the water soluble phenol resin of tertiary amine oxide side group, step is as follows:
1. 10 parts of epoxy phenolicss are dissolved in 10-50 part organic solvent, and system are cooled to about 10 ℃ with mixture of ice and water; In nitrogen protection with under constantly stirring, slow Dropwise 5-20 part dimethylamine agueous solution (or diethylamine); After dropwising, continue room temperature reaction 2-24h; At last, system temperature is risen to 60 ℃ continue reaction 2-24h, obtain light yellow homogeneous liquid;
2. remove nitrogen protection, in above-mentioned system, add the citric acid of 0.5-5 part, stir and make it dissolving; System temperature is transferred to 60-90 ℃, slowly the H of Dropwise 5-10 part
2O
2(30% aqueous solution), about 1-5h finishes, during controlled temperature between 60～80 ℃; Then system temperature is risen to 85 ℃ and continue stirring reaction 5-10h, be chilled to room temperature, obtain almost colourless thick homogeneous liquid; Aforesaid liquid is moved in the vacuum distillation apparatus, and decompression steams the solvent of the overwhelming majority, obtains the light yellow solid thing.
In the method, it is as follows to contain the chemical reaction process of resol of tertiary amine oxide side group:
A kind of optimal technical scheme, it is characterized in that: the organic solvent in the described step (1) is acetone, tetrahydrofuran (THF), dioxane, ethyl acetate, ethylene glycol monoemethyl ether, N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide and composition thereof.
Another object of the present invention provides the application of above-mentioned water soluble phenol resin.
Above-mentioned purpose of the present invention reaches by the following technical programs:
The application of described water soluble phenol resin in thermosensitive imaging system.
Water soluble phenol resin of the present invention, can be applied in the middle of the thermosensitive imaging system through following 3 steps, (1) coating: and other materials (Infrared dyes, flow agent etc.) are used, be mixed with coating fluid with water as solvent, be coated in (base material can be metal sheet, sheet glass or organic polymer material) on the substrate surface; (2) pre-roasting version: aqueous solvent is evaporated the coated film that has certain degree of hardness with formation; (3) exposure: use the infrared equipment exposure-processed, make the resin generation thermolysis of seeing the light part to cause the exposure region dissolving resin to change; (4) develop in neutral water through the resin film after the overexposure, can obtain the negative type image.
Beneficial effect:
Water soluble phenol resin of the present invention is characterized in that the soluble in water and intensive polar solvent of this resin, the modest viscosity of solution, shelf-stable; This resin solution is easy to coating film forming, the satisfactory mechanical property of film; This resin is stable below 140 ℃, and decomposing fast more than 150 ℃, and resin becomes non-water-solublely by water-soluble, and single degradation production still dissolves in organic solvent; This resin and infrared sensitizing dye and other auxiliary agent are used, and can prepare the temperature-sensitive coating of infrared laser imaging.Table 1 is the fundamental property of typical water dissolubility phenol resin solution of the present invention.
The solubility property of table 1 tertiary amine oxide resol
| Solvent | Novolac epoxy | The tertiary amine oxide resin | 160 ℃ of heating 1min |
| Water | Insoluble | Dissolving | Insoluble |
| Ethanol | Insoluble | Insoluble | Insoluble |
| Acetone | Dissolving | Insoluble | Dissolving |
| Methylene dichloride | Dissolving | Insoluble | Dissolving |
| N, dinethylformamide | Dissolving | Dissolving | Dissolving |
| N,N-dimethylacetamide | Dissolving | Dissolving | Dissolving |
| The monomethyl pyrrolidone | Dissolving | Dissolving | Dissolving |
The characteristic of table 2 tertiary amine oxide resol
| Character | Performance index | Index | Explanation |
| Outward appearance | Light yellow | ||
| Limiting viscosity | gdL -1 | 0.2-1.2 | |
| Stability in storage | 25℃ | 12 months | Any variation does not take place |
| Water-intake rate | ％ | 1-20％ | With changes in environmental conditions |
| Heat decomposition temperature | 140-170 |
The constructional feature of table 3 tertiary amine oxide resol
| The position | Feature |
| Main chain | The phenolic material |
| Side group | The tertiary amine group that contains nitrogen-oxygen bond |
| Remarkable functional group | Nitrogen-oxygen bond |
The water soluble phenol resin that side chain of the present invention contains the tertiary amine oxide group has following characteristics: (1) is easy to preparation, and is water-soluble good; (2) resin is a non-ionic polymers, not metal ion and halogen ion; (3) because the tertiary amine oxide group more stable below 140 ℃, and is being easy to more than 150 ℃ to decompose and degradation production does not have gas, therefore can be used as the temperature-sensitive functional materials; (4) hypotoxicity.
Water soluble phenol resin involved in the present invention is used for thermosensitive imaging system owing to contain the very strong nitrogen-oxygen bond of polarity, and wetting ability is fine.Under the effect of heat or infrared light, nitrogen-oxygen bond can rupture again, and to be transformed into water insoluble from water-soluble to make resin, so just makes exposed portion and unexposed portion produce bigger dissolubility difference, thereby present a contrast.After utilizing solvent (water) to dissolve exposure (unexposed) part, can obtain needed figure, finish photologging.
Below by the drawings and specific embodiments the present invention is done further, but and do not mean that limiting the scope of the invention.
Description of drawings
1 figure is the SEM photo of the embodiment of the invention 1 resulting image.
Embodiment
Example 1:
The preparation of the water soluble phenol resin of 2-(cacodyl oxide amido) acetate modification
2-dimethylin acetate and deionized water are added in the single port bottle, and hydrogen peroxide joins in the dropping funnel.The pH value of reaction Pretesting system is about 8.5.Because heating makes system temperature be elevated to 75 ℃, opens the piston of dropping funnel then, hydrogen peroxide is added drop-wise in the 2-dimethylin acetic acid solution lentamente goes.That system temperature is not obviously risen to is suitable for the control rate of addition, general 5-6 second/drip.Dropwise, keep 75 ℃ to stir half hour, be warming up to 80 ℃, continue to stir 4 hours.Stop heating, be cooled to room temperature.The pH value of test system is about 6.Drip the aqueous solution of sodium bisulfite of 1.1 grams, stir 2h, with removing unreacted hydrogen peroxide.Down remove moisture in the system in 70 ℃ as far as possible, obtain ruddy semi-solid thing with the water pump underpressure distillation.To distill the resulting product in back and be dissolved in ethanol,, filter, and then can remove unnecessary bisulfite and receive because sodium bisulfite is insoluble to ethanol.Under 50 ℃, ethanol is steamed with revolving the steaming method.Obtain 2-(cacodyl oxide amido) acetate.
Novolac epoxy is added in the there-necked flask, and heating makes its fusing, adds the N-N-methyl-2-2-pyrrolidone N-, stirs, and makes resin dissolves.Load weighted oxidized 2-dimethylin acetate is put into Erlenmeyer flask, add minor N-N-methyl-2-2-pyrrolidone N-it is dissolved, and join in the solution of above-mentioned nitrogen oxidation 2-dimethylin acetate.System temperature is risen to 80 ℃, and stirring reaction 4 hours obtains transparent light yellow thick liquid.Use the oil pump underpressure distillation down at 70 ℃, remove most of solvent, obtain the water soluble phenol resin of 3-(cacodyl oxide amido) propionic acid modification.
In the infrared sensitizing dye of this tertiary amine oxide resin of 2.0g and 30mg and ethylene glycol monomethyl ether that 0.2gPVA1788 is dissolved in 20ml, it is dissolved fully obtain the mazarine homogeneous phase solution.This solution is adopted the spin-coating method coating or adopts the excellent blade coating mode of silk to apply the one layer of polymeric film at the aluminium plate base through anodic oxidation treatment, place dry under the normal temperature.Utilize the 830nm infrared laser exposure, exposure energy is 400mJ/cm
2Develop with distilled water, in 100 ℃ of dryings, obtain final image then.The volumetric shrinkage of figure＜10% can not occur subsiding, degradation phenomena such as distortion.
SEM photo by the image that obtains behind exposure and the water development is referring to accompanying drawing 1.The energy density of laser explosure is about 400mJ/cm
2Gray area is aluminium plate base (unexposed area), and black stripe is the resin that the exposure area stays behind water development.The thickness that resin is thin is 2.4 μ m, the about 50 μ m of line thickness.As can be seen, unexposed area is fully by flush away, but not the exposure area stays on edition base, and the edge of figure line is regular.
Example 2:
The preparation of the water soluble phenol resin of 3-(cacodyl oxide amido) propionic acid modification
Dimethylamine is added in the there-necked flask, be chilled to about 5 ℃ with ice-water bath.Then under agitation, methyl acrylate is added drop-wise in the reaction system.The exothermic heat of reaction phenomenon is obvious, and the control rate of addition makes temperature be no more than 10 ℃.After methyl acrylate drips, remove ice-water bath, stir 16h under the room temperature.In 60 ℃ of water-baths, heat 6h then.Most water of pressure reducing and steaming and unreacted raw material, a large amount of white solids are separated out in cooling.With the material that obtains after concentrating in vacuum drying oven dry 10 hours, temperature was 80 ℃.So just obtain the product 3-dimethylamino propionic acid tested.Resulting product is a 3-dimethylin propionic acid, fusing point 126-127 ℃.FT-IR：3330，2700-2250，1470，1380，1650-1550。
3-dimethylin propionic acid and deionized water are added in the single port bottle, and hydrogen peroxide joins in the dropping funnel.The pH value of reaction Pretesting system is about 8.5.Because heating makes system temperature be elevated to 75 ℃, opens the piston of dropping funnel then, hydrogen peroxide is added drop-wise in the 3-dimethylin propionic acid solution lentamente goes.The speed that liquid in the dropping funnel is emitted can not be too fast, and it is suitable that rate of addition does not obviously rise to system temperature, general 5-6 second/drip.After dripping end, keep 75 ℃ to stir half hour, temperature is risen to 80 ℃ then, stirred aging 4 hours.Stop heating, be cooled to room temperature.The pH value of test system is 6.Drip the aqueous solution of sodium bisulfite of 1.1 grams, stir 2h, with removing unreacted hydrogen peroxide.Down remove moisture in the system in 70 ℃ as far as possible, obtain ruddy semi-solid thing with the water pump underpressure distillation.To distill the resulting product in back and be dissolved in ethanol,, filter, and then can remove unnecessary bisulfite and receive because sodium bisulfite is insoluble to ethanol.Under 50 ℃, ethanol is steamed with revolving the steaming method.Obtain 3-(cacodyl oxide amido) propionic acid.FT-IR：3330，2700-2250，1470，1380，980，922。
Earlier novolac epoxy is added in the there-necked flask, heating makes its fusing, adds the N-N-methyl-2-2-pyrrolidone N-, stirs, and makes resin dissolves.Load weighted oxidized 3-dimethylin propionic acid is put into Erlenmeyer flask, add minor N-N-methyl-2-2-pyrrolidone N-it is dissolved, and join in the solution of above-mentioned nitrogen oxidation 3-dimethylin propionic acid.System temperature is risen to 80 ℃, and stirring reaction 4 hours obtains transparent light yellow thick liquid.Use the oil pump underpressure distillation down at 70 ℃, remove most of solvent, obtain the water soluble phenol resin of 3-(cacodyl oxide amido) propionic acid modification.
In the infrared sensitizing dye of this tertiary amine oxide resin of 2.0g and 30mg and tetrahydrofuran (THF) that 0.2gPVA1788 is dissolved in 20ml, it is dissolved fully obtain the mazarine homogeneous phase solution.Adopt spin-coating method coating or the excellent blade coating mode of silk to apply the one layer of polymeric film at the aluminium plate base through anodic oxidation treatment this solution, normal temperature placement down is dry.Utilize the 830nm infrared laser exposure, exposure energy is 400mJ/cm
2Develop with distilled water, in 100 ℃ of dryings, obtain final image then.The volumetric shrinkage of figure＜10% can not occur subsiding, degradation phenomena such as distortion.
Example 3:
Oxidation N, the preparation of the water soluble phenol resin of N dimethylamine yl benzoic acid modification
Adopt two-step approach synthesizing water-solubility resol.At first synthetic N, the oxide compound of N dimethylamine yl benzoic acid.Add N in the 100ml four-hole boiling flask of magneton stirring, prolong, thermometer is housed, (8.25g, 0.05mol), ethanol (20ml), heated and stirred makes dissolving to the N dimethylamine yl benzoic acid.After temperature of reaction system rises to 75 ℃, slowly drip hydrogen peroxide (6.23g, 0.055mol).In the process that drips, controlled temperature is between 75～80 ℃, and about 1h dropwises.Afterwards, continue reaction 4～6h in 80 ± 2 ℃.Stop heating, the system for the treatment of is cooled to room temperature, and suction filtration gets the powdery solid, and 50 ℃ of dry 4h in the vacuum drying oven get product 5.7g (productive rate 63%).Mp: do not measure (154 ℃ of decomposition).FT-IR(KBr，cm
-1)：3410，3108，3070，3023，2966，2966，2873，1676，1578，1446，1354，1290，1230，970。
1H NMR(D
2O，δppm)：8.22(s，1H)，7.88-7.96(m，2H)，7.54-7.61(m，3H)，3.76(s，6H)。
In the 100ml four-hole boiling flask of magneton stirring, prolong, thermometer is housed, add oxidation N, N dimethylamine yl benzoic acid (1.59g, 0.01mol), deionized water (10ml), after the stirring and dissolving, add novolac epoxy (2g) and dioxane (20ml), stirring and dissolving.Be warming up to 80 ℃, reaction 8h.After reaction finished, underpressure distillation was desolvated, and obtains pink colour pulverulent solids resin, i.e. water soluble phenol resin.
In the infrared sensitizing dye of this tertiary amine oxide resin of 2.0g and 35mg and 90% ethanolic soln that 0.2gPVA1788 is dissolved in 20ml, it is dissolved fully obtain the mazarine homogeneous phase solution.This solution is adopted the spin-coating method coating or adopts the excellent blade coating mode of silk to apply the one layer of polymeric film at the aluminium plate base through anodic oxidation treatment, place dry under the normal temperature.Utilize the 830nm infrared laser exposure, exposure energy is 350mJ/cm
2Develop with distilled water, in 100 ℃ of dryings, obtain final image then.The volumetric shrinkage of figure＜10% can not occur subsiding, degradation phenomena such as distortion.
Example 4:
The oxidation of dimethyl tertiary amine resol prepares water soluble phenol resin
The 4g epoxy phenolics is dissolved in the dioxane of 20ml, under condition of ice bath, adds 3.6g dimethylamine agueous solution (30%), stir 16h, then at 60 ℃ of reaction 6h down.Underpressure distillation removes and anhydrates and dioxane, obtains light yellow powdery solid (A).
5.1g material (A) and 0.2g citric acid are dissolved in the dioxane of 20ml, be heated to 75 ℃ after, drip 2.2g aqueous hydrogen peroxide solution (30%), drip 75～80 ℃ of process temperature controls, about 1h of time.Hydrogen peroxide adds the back in 80 ± 2 ℃ of aging 4～6h.After reaction finished, underpressure distillation obtained glassy yellow powdery resin (B).FT-IR(KBr，cm
-1)：3500，2820，2773，1600，1500，1250，1030，967。
In the infrared sensitizing dye of the tertiary amine oxide resin of 2.0g and 30mg and tetrahydrofuran (THF) that 0.2gPVA1788 is dissolved in 20ml, it is dissolved fully obtain the mazarine homogeneous phase solution.Adopt spin-coating method coating or the excellent blade coating mode of silk to apply the one layer of polymeric film at the aluminium plate base through anodic oxidation treatment this solution, normal temperature placement down is dry.Utilize the 830nm infrared laser exposure, exposure energy is 400mJ/cm
2Develop with distilled water, in 100 ℃ of dryings, obtain final image then.The volumetric shrinkage of figure＜10% can not occur subsiding, degradation phenomena such as distortion.
Example 5:
The oxidation of diethyl tertiary amine resol prepares water soluble phenol resin
With the 4g epoxy phenolics be dissolved in 20ml-dioxane, under ice bath, add 5.8g diethylamine aqueous solution (30%), stir 16h, then at 60 ℃ of reaction 6h down.Underpressure distillation removes and anhydrates and dioxane, obtains light yellow powdery solid (A).
5.5g material (A) and 0.2g citric acid are dissolved in the dioxane of 20ml, be heated to 75 ℃ after, drip 2.1g aqueous hydrogen peroxide solution (30%), drip 75～80 ℃ of process temperature controls, about 1h of time.Hydrogen peroxide adds the back in 80 ± 2 ℃ of aging 4～6h.After reaction finished, underpressure distillation obtained glassy yellow powdery resin (B).FT-IR(KBr，cm
-1)：3502，2824，2775，1601，1500，1252，1030，965。
In the infrared sensitizing dye of this tertiary amine oxide resin of 2.0g and 30mg and tetrahydrofuran (THF) that 0.2gPVA1788 is dissolved in 20ml, it is dissolved fully obtain the mazarine homogeneous phase solution.Adopt spin-coating method coating or the excellent blade coating mode of silk to apply the one layer of polymeric film at the aluminium plate base through anodic oxidation treatment this solution, normal temperature placement down is dry.Utilize the 830nm infrared laser exposure, exposure energy is 400mJ/cm
2Develop with distilled water, in 100 ℃ of dryings, obtain final image then.The volumetric shrinkage of figure＜10% can not occur subsiding, degradation phenomena such as distortion.
Claims (8)
1. water soluble phenol resin, its chemical structure is as follows:
Wherein: A be methylene radical ,-CH
2COO-,-CH
2CH
2COO-,-C
6H
5COO-; B is methyl, ethyl; C is methyl, ethyl; Its number-average molecular weight is 900-10000, and oxirane value is between 0.20-0.55mol/100g.
2. the preparation method of the described water soluble phenol resin of claim 1, step is as follows:
(1) organic acid that 10-55 part is contained the tertiary amine oxide group dissolves in the organic solvent of 10-100 part and generates corresponding solution (1);
(2) 100 parts of epoxy phenolicss are dissolved generation corresponding solution (2) in 70-200 part organic solvent;
(3),, obtain water soluble phenol resin solution at 50-100 ℃ of following stirring reaction 1-10 hour with solution (1) and solution (2).
3. the preparation method of water soluble phenol resin according to claim 2, it is characterized in that: the organic acid that contains the tertiary amine oxide group described in the described step (1) means the organic compound with following chemical structure:
4. the preparation method of water soluble phenol resin according to claim 3, it is characterized in that: the organic solvent in described step (1) and (2) is acetone, tetrahydrofuran (THF), dioxane, ethyl acetate, ethylene glycol monoemethyl ether, N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide and composition thereof.
5. the preparation method of the described water soluble phenol resin of claim 1, step is as follows:
(1). 10 parts of epoxy phenolicss are dissolved in 10-50 part organic solvent, and system are cooled to about 10 ℃ with mixture of ice and water; In nitrogen protection with under constantly stirring, slow Dropwise 5-20 part dimethylamine agueous solution or diethylamine; After dropwising, continue room temperature reaction 2-24h; At last, system temperature is risen to 60 ℃ continue reaction 2-24h, obtain light yellow homogeneous liquid;
(2). remove nitrogen protection, in above-mentioned system, add the citric acid of 0.5-5 part, stir and make it dissolving; System temperature is transferred to 60-90 ℃, slowly the H of Dropwise 5-10 part
2O
230% the aqueous solution, about 1-5h finishes, during controlled temperature between 60～80 ℃; Then system temperature is risen to 85 ℃ and continue stirring reaction 5-10h, be chilled to room temperature, obtain almost colourless thick homogeneous liquid; Aforesaid liquid is moved in the vacuum distillation apparatus, and decompression steams the solvent of the overwhelming majority, obtains the light yellow solid thing.
6. the preparation method of water soluble phenol resin according to claim 5, it is characterized in that: the organic solvent in the described step (1) is acetone, tetrahydrofuran (THF), dioxane, ethyl acetate, ethylene glycol monoemethyl ether, N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide and composition thereof.
7. the application of the described water soluble phenol resin of claim 1 in thermosensitive imaging system.
8. the application of water soluble phenol resin according to claim 7 in thermosensitive imaging system, its concrete steps are as follows: (1) coating: be used with Infrared dyes, flow agent, be mixed with coating fluid with water as solvent, be coated on the substrate surface; (2) pre-roasting version: aqueous solvent is evaporated the coated film that has certain degree of hardness with formation; (3) exposure: use the infrared equipment exposure-processed, make the resin generation thermolysis of seeing the light part to cause the exposure region dissolving resin to change; (4) develop in neutral water through the resin film after the overexposure, obtain the negative type image.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659993A (en) * | 2012-04-12 | 2012-09-12 | 上海大学 | Processing-free temperature-sensitive film forming resin for CTP plates, and preparation method thereof |
| WO2013127227A1 (en) * | 2012-02-29 | 2013-09-06 | 华南理工大学 | Amine-oxide-group-containing conjugated polymer photoelectric material and application thereof |
-
2007
- 2007-10-18 CN CN2007101760793A patent/CN101139427B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013127227A1 (en) * | 2012-02-29 | 2013-09-06 | 华南理工大学 | Amine-oxide-group-containing conjugated polymer photoelectric material and application thereof |
| US9159928B2 (en) | 2012-02-29 | 2015-10-13 | South China University Of Technology | Amine-oxide-group-containing conjugated polymer photoelectric material and use thereof |
| CN102659993A (en) * | 2012-04-12 | 2012-09-12 | 上海大学 | Processing-free temperature-sensitive film forming resin for CTP plates, and preparation method thereof |
| CN102659993B (en) * | 2012-04-12 | 2013-12-25 | 上海大学 | Processing-free temperature-sensitive film forming resin for CTP plates, and preparation method thereof |
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