CN101696265B - Polycondensate resin of pyrogallol and divinylbenzene and synthesis method thereof - Google Patents
Polycondensate resin of pyrogallol and divinylbenzene and synthesis method thereof Download PDFInfo
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- CN101696265B CN101696265B CN2009102365841A CN200910236584A CN101696265B CN 101696265 B CN101696265 B CN 101696265B CN 2009102365841 A CN2009102365841 A CN 2009102365841A CN 200910236584 A CN200910236584 A CN 200910236584A CN 101696265 B CN101696265 B CN 101696265B
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- pyrogallol
- vinylstyrene
- divinyl benzene
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Abstract
The invention discloses a polycondensate resin of pyrogallol and divinylbenzene and a synthesis method thereof, which belong to the technical field of preparing functional polymers. The polycondensate resin of the pyrogallol and the divinylbenzene synthesized by the method has the following structural general formula, wherein n is between 2 and 15. In the synthesis method, the pyrogallol, the divinylbenzene and a catalyst perform refluxing reactions to obtain the polycondensate resin of the pyrogallol and the divinylbenzene. The polycondensate resin of the pyrogallol and the divinylbenzene has the advantages of high purity, low free phenol and volatile matter, high softening point and high transparency, and can be used in the industries of printing, electronics, coating, printing ink and the like.
Description
Technical field
The design that the present invention relates to one type of new type resin is with synthetic, and the design of particularly a kind of pyrogallol and divinyl benzene polycondensate is with synthetic.
Background technology
Resin is to realize industrialized macromolecular compound in the world the earliest, so far the history of existing last 100 years.Because its raw material is easy to get, cheap, moulding process property is good, has excellent mechanical property, flame retardant resistance and thermotolerance etc.So it has become the indispensable starting material of contemporary industry, especially obtained using widely in industries such as printing, electronics, coating and printing ink.And prior resin exists that thermotolerance is not enough, fragility big and defective such as poor toughness.
Summary of the invention
In view of above-mentioned prior art situation, contriver of the present invention is carrying out intensive research to common resol and phenol resins, synthesizes one type of brand-new pyrogallol and divinyl benzene polycondensate.This compounds can be used for industries, particularly lithography industry such as printing, electronics, coating and printing ink as novel high polymer.
Pyrogallol provided by the invention and divinyl benzene polycondensate are synthetic by pyrogallol, Vinylstyrene and catalyzer, and it has following general formula:
Wherein n is 2-15.
Concrete preparation method of the present invention is divided into has solvent method and solventless method.
Solvent method is arranged: in the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol, catalyzer and solvent under the nitrogen protection; The solvent of 100-300 parts by volume adds 15-50 weight part pyrogallol; 0.2-1 the catalyzer of weight part, raw material dissolve the Vinylstyrene that the back drips the 10-80 parts by volume, 70-95 ℃ of back flow reaction fully; Behind the reaction 3-15h; Heat up and distill moisture, solvent and unreacted raw material, become liquid, obtain pyrogallol and divinyl benzene polycondensate up to resin;
Solventless method: in the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol and catalyzer under the nitrogen protection, solvent-free, 15-50 weight part pyrogallol adds the catalyzer of 0.2-1 weight part; Drip the Vinylstyrene of 10-80 parts by volume; 70-95 ℃ of back flow reaction, behind the reaction 3-15h, distillation moisture and unreacted raw material heat up; Become liquid up to resin, obtain pyrogallol and divinyl benzene polycondensate;
The relation of said weight part and parts by volume is g/ml or kg/l.
Described catalyzer is tosic acid, oxalic acid, hydrochloric acid, trichoroacetic acid(TCA) or phosphoric acid, preferably phosphoric acid or oxalic acid.
Described solvent is an OOS, comprises toluene, YLENE, perhaps contains the organic solvent of halogen, comprises 1, and 2-ethylene dichloride, trichloromethane, tetrachloromethane, 1,2-dichloroethene are preferred 1,2-ethylene dichloride or YLENE.
Described Vinylstyrene is 1,3-Vinylstyrene, 1, one or both in the 4-Vinylstyrene.
Synthetic pyrogallol of the present invention and divinyl benzene polycondensate have following advantage: be connected with three hydroxyls on the phenyl ring of pyrogallol, character is more active, easy and nucleophilic reagent generation chemical reaction; With pyrogallol synthetic resin since the content of hydroxyl than higher, higher than common resol or phenol resins solubleness in alkaline aqueous solution, in practical application, have particular performances; The pyrogallol that the present invention produces and divinyl benzene polycondensate purity height, free phenol and fugitive constituent are low, and softening temperature is high, and transparency is high, can be used as novel high polymer and is used for industries, particularly lithography industry such as printing, electronics, coating and printing ink.
Below in conjunction with embodiment, the present invention is done further description, rather than limit scope of the present invention.
Embodiment
Embodiment 1:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 15.0g under the nitrogen protection, add 100mL toluene, 0.2g oxalic acid; Raw material dissolves the back fully and drips 15.0mL 1, and the 3-Vinylstyrene is behind 70 ℃ of back flow reaction 5h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 2:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 16.0g under the nitrogen protection, add 200mL 1, the 2-ethylene dichloride; 0.4g dissolving the back fully, tosic acid, raw material drip 20.0mL 1,4-Vinylstyrene; Behind 75 ℃ of back flow reaction 10h, heat up distillation moisture, solvent and unreacted raw material become liquid up to resin; Pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 3:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 18.0g under the nitrogen protection, add 150mL YLENE, 0.6g hydrochloric acid; Raw material dissolves the back fully and drips 25.0mL 1, and the 4-Vinylstyrene is behind 80 ℃ of back flow reaction 8h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 4:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 19.5g under the nitrogen protection, add 250mL toluene, the 0.8g tosic acid; Raw material dissolves the back fully and drips 30.0mL 1, and the 3-Vinylstyrene is behind 70 ℃ of back flow reaction 15h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 5:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 20.0g under the nitrogen protection, add the 300mL trichloromethane, 1.0g phosphoric acid; Raw material dissolves the back fully and drips 40.0mL 1, and the 4-Vinylstyrene is behind 75 ℃ of back flow reaction 13h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 6:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 22.0g under the nitrogen protection, add the 200mL tetrachloromethane, the 0.95g trichoroacetic acid(TCA); Raw material dissolves back Dropwise 5 0.0mL 1 fully, and the 3-Vinylstyrene is behind 90 ℃ of back flow reaction 6h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 7:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 25.0g under the nitrogen protection, add the 100mL 1,2-dichloroethene; 0.85g dissolving the back fully, hydrochloric acid, raw material drips 60.0mL 1,3-Vinylstyrene; Behind 95 ℃ of back flow reaction 3h, heat up distillation moisture, solvent and unreacted raw material become liquid up to resin; Pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 8:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 27.5g under the nitrogen protection, add 200mL YLENE, 0.75g oxalic acid; Raw material dissolves the back fully and drips 70.0mL 1, and the 3-Vinylstyrene is behind 80 ℃ of back flow reaction 9h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 9:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 29.5g under the nitrogen protection, add 300mL toluene, the 0.55g tosic acid; Raw material dissolves the back fully and drips 80.0mL 1, and the 4-Vinylstyrene is behind 85 ℃ of back flow reaction 6h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 10:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 30.4g under the nitrogen protection, add 150mL 1, the 2-ethylene dichloride; 0.45g dissolving the back fully, phosphoric acid, raw material drips 75.0mL 1,4-Vinylstyrene; Behind 75 ℃ of back flow reaction 8h, heat up distillation moisture, solvent and unreacted raw material become liquid up to resin; Pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 11:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 32.4g under the nitrogen protection, add 250mL toluene, the 0.35g trichoroacetic acid(TCA); Raw material dissolves back Dropwise 5 5.0mL 1 fully, and the 3-Vinylstyrene is behind 90 ℃ of back flow reaction 7h; Distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 12:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 33.5g under the nitrogen protection, add 300mL YLENE, 0.25g hydrochloric acid; Raw material dissolves the back fully and drips 20mL 1, the 3-Vinylstyrene, and 20mL 1; The 4-Vinylstyrene, behind 80 ℃ of back flow reaction 9h, distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 13:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 35.0g under the nitrogen protection, add 150mL YLENE, 0.9g oxalic acid, raw material dissolve the back fully and drip 20mL 1; The 3-Vinylstyrene, 30mL 1, the 4-Vinylstyrene; Behind 80 ℃ of back flow reaction 10h, behind the reaction 5h, distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 14:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 37.5g under the nitrogen protection, add 250mL 1,2-ethylene dichloride, 0.8g oxalic acid; Raw material dissolves the back fully and drips 30mL 1, the 3-Vinylstyrene, and 20mL 1; The 4-Vinylstyrene, behind 70 ℃ of back flow reaction 12h, distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 15:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 40.0g under the nitrogen protection, add 200mL YLENE, 0.6g oxalic acid; Raw material dissolves the back fully and drips 15mL 1, the 3-Vinylstyrene, and 55mL 1; The 4-Vinylstyrene, behind 75 ℃ of back flow reaction 13h, distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 16:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 42.5g under the nitrogen protection, add 250mL toluene, 0.7g phosphoric acid; Raw material dissolves the back fully and drips 25mL1, the 3-Vinylstyrene, and 35mL 1; The 4-Vinylstyrene, behind 85 ℃ of back flow reaction 12h, distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 17:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 45.0g under the nitrogen protection, add 200mL 1,2-ethylene dichloride, 0.3g phosphoric acid; Raw material dissolves the back fully and drips 10mL 1, the 3-Vinylstyrene, and 60mL 1; The 4-Vinylstyrene, behind 70 ℃ of back flow reaction 15h, distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 18:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 49.5g under the nitrogen protection, add 300mL YLENE, 0.5g oxalic acid; Raw material dissolves the back fully and drips 60mL 1, the 3-Vinylstyrene, and 10mL 1; The 4-Vinylstyrene, behind 85 ℃ of back flow reaction 11h, distillation moisture, solvent and unreacted raw material heat up; Become liquid up to resin, pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 19:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 20.0g under the nitrogen protection, 0.5g oxalic acid drips 30.0mL 1; The 3-Vinylstyrene; Behind 75 ℃ of back flow reaction 12h, heat up distillation moisture and unreacted raw material become liquid up to resin; Pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Embodiment 20:
In the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol 30.4g under the nitrogen protection, 0.75g phosphoric acid drips 45.0mL 1; The 4-Vinylstyrene; Behind 90 ℃ of back flow reaction 8h, heat up distillation moisture and unreacted raw material become liquid up to resin; Pour out reaction flask, obtain pyrogallol and divinyl benzene polycondensate.
Claims (6)
1. pyrogallol and divinyl benzene polycondensate is characterized in that described Vinylstyrene is 1,3-Vinylstyrene Huo and 1, and the 4-Vinylstyrene, it has following general formula:
Wherein n is 2-15.
2. the compound method of pyrogallol as claimed in claim 1 and divinyl benzene polycondensate is characterized in that, its concrete preparation method is: in the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol, catalyzer and solvent under the nitrogen protection; The solvent of 100-300 parts by volume adds 15-50 weight part pyrogallol, and the catalyzer of 0.2-1 weight part, raw material dissolve the back fully and drip 1 of 10-80 parts by volume; The 3-Vinylstyrene or and 1,4-Vinylstyrene, 70-95 ℃ of back flow reaction; Behind the reaction 3-15h; Heat up and distill moisture, solvent and unreacted raw material, become liquid, obtain pyrogallol and 1 up to resin; The 3-Vinylstyrene or and 1, the 4-divinyl benzene polycondensate;
The relation of said weight part and parts by volume is g/ml or kg/l.
3. the compound method of pyrogallol as claimed in claim 1 and divinyl benzene polycondensate is characterized in that, its concrete preparation method is: in the four-hole bottle that has whisking appliance, prolong, constant pressure funnel and TM, add pyrogallol and catalyzer under the nitrogen protection; Solvent-free, 15-50 weight part pyrogallol adds the catalyzer of 0.2-1 weight part, drips 1 of 10-80 parts by volume; The 3-Vinylstyrene or and 1,4-Vinylstyrene, 70-95 ℃ of back flow reaction; Behind the reaction 3-15h, heat up distillation moisture and unreacted raw material become liquid up to resin; Obtain pyrogallol and 1, the 3-Vinylstyrene or and 1, the 4-divinyl benzene polycondensate;
The relation of said weight part and parts by volume is g/ml or kg/l.
4. according to the compound method of claim 2 or 3 described pyrogallols and divinyl benzene polycondensate, it is characterized in that described catalyzer is tosic acid, oxalic acid, hydrochloric acid, trichoroacetic acid(TCA) or phosphoric acid.
5. the compound method of pyrogallol according to claim 2 and divinyl benzene polycondensate is characterized in that, described solvent is toluene or YLENE.
6. the compound method of pyrogallol according to claim 2 and divinyl benzene polycondensate is characterized in that, described solvent is 1,2-ethylene dichloride, trichloromethane, tetrachloromethane or 1,2-dichloroethene.
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| CN2009102365841A CN101696265B (en) | 2009-10-30 | 2009-10-30 | Polycondensate resin of pyrogallol and divinylbenzene and synthesis method thereof |
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| CN2009102365841A CN101696265B (en) | 2009-10-30 | 2009-10-30 | Polycondensate resin of pyrogallol and divinylbenzene and synthesis method thereof |
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| CN1347869A (en) * | 2001-09-05 | 2002-05-08 | 北京师范大学 | Synthesis of ester ether compound with high acidolysis activity |
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| CN1347869A (en) * | 2001-09-05 | 2002-05-08 | 北京师范大学 | Synthesis of ester ether compound with high acidolysis activity |
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