CN1557845A - Process for synthesizing catechol modified terpene resin - Google Patents
Process for synthesizing catechol modified terpene resin Download PDFInfo
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- CN1557845A CN1557845A CNA2004100127066A CN200410012706A CN1557845A CN 1557845 A CN1557845 A CN 1557845A CN A2004100127066 A CNA2004100127066 A CN A2004100127066A CN 200410012706 A CN200410012706 A CN 200410012706A CN 1557845 A CN1557845 A CN 1557845A
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- pyrocatechol
- modified terpene
- terpene resin
- resin
- add
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Abstract
The present invention relates to the synthesis process of catechol modified terpene resin. Terpene resin and catechol are dissolved in solvent and catalyzed with AlCl3; and through separating the supper layer of organic matter, washing, separation and drying, catechol modified terpene resin is obtained. The catechol modified terpene resin thus produced has very powerful corrosion resistance and durability, and may be used as paint material.
Description
Technical field
The present invention relates to a kind of resin, particularly a kind of synthetic method of pyrocatechol modified terpene resin.
Background technology
Terpine resin, terpene phenolic resin are the abundant rosin Chemicals of china natural resources, has superior anti-oxidant and thermal stability, with natural rubber good consistency is arranged, be used widely industrial as tackifier, but reaction active groups is few in these two kinds of resins, film forming properties is poor, has limited its use in other fields such as coating.Therefore, the functionalizing compound terpine resin that induces one is obtained the modified terpene resin of various performances, can widen the Application Areas of terpine resin, for the turps deep processing and utilization is opened up new approach.
The war of inventor's ecliptic, Lei Fuhou etc. had once published the article of " synthesizing and performance study of terpenes-pyrocatechol resin " at " chemistry of forest product and industry " 2003,23 (1), with CuCl
2Be catalyzer, turps, pyrocatechol are that raw material has synthesized terpenes-pyrocatechol resin (being called for short TCR).Find in the physical and chemical performance research to this polymer resin, it is soluble in organic solvent, compare with terpine resin with the terpene phenolic resin, film forming properties improves greatly, possessed the basic characteristics as coating, but also there is weak point in the synthetic method of the described terpenes of article-pyrocatechol resin,, resin color and luster higher as temperature of reaction is darker etc., for this reason, need improve the synthetic method of terpenes-pyrocatechol resin from aspects such as raw material, reaction conditionss.
Summary of the invention
The inventor is on the basis of above-mentioned disclosed article, adopt new raw material and reaction process, performance to the gained resin has been carried out many researchs and test, particularly its synthesis technique has been carried out many-sided discussion, has obtained can be used for the pyrocatechol modified terpene resin of coating.
Technical scheme of the present invention is achieved in that
Terpine resin is ground, be put in the reactor of whipping appts, add the pyrocatechol of pressing terpine resin part by weight 10-20%,, add anhydrous AlCl with 1～3 times dissolution with solvents
3Catalyzer, catalyst levels account for 5～25% of reaction-ure mixture, and temperature is controlled at 80 to 85 ℃ of reactions 3-8 hour, cooling adds water and continues to stir, to destroy the complex compound of chlorine, after adding hydrochloric acid again and stirring for some time, standing demix, isolating the upper strata is organic layer, use the NaCl solution washing, wash twice again with water, separate obtaining organic layer, drying, obtain the pyrocatechol modified terpene resin at last, can be as the raw material of filming of coating.
The solvent of above-described dissolving terpine resin and pyrocatechol is selected in gasoline and benzene, toluene, kerosene, ethyl acetate, perhaps selects mixed solvent for use.
The NaCl solution of above-described washing pyrocatechol modified terpene resin is the saturated NaCl solution of heat.
The material of above-described dry pyrocatechol modified terpene resin is an anhydrous Na
2SO
4
The present invention has the following advantages:
1, pyrocatechol modified terpene resin and raw lacquer have stronger reactivity and consistency, can be as the raw material of coating, if in raw lacquer, add the pyrocatechol modified terpene resin, can reduce the cost of raw lacquer coating, will replace the status of raw lacquer in modern coating, make people use of fine quality, inexpensive coating, this will have great importance.
2. the basic raw material of synthesizing o-dihydroxybenzene modified terpene resin is terpine resin and pyrocatechol, and it is bigger than the molecular weight that with turps, pyrocatechol is raw material synthetic pyrocatechol-terpine resin, is more suitable for the raw material as coating.
Embodiment
Embodiment 1
Take by weighing the terpine resin of 120 grams, porphyrize adds 12 gram pyrocatechols in the 1000ml triangular flask again, with 260ml gasoline dissolving, load onto spherical condensation tube and thermometer, heating and stir in electric mantle with electric power, when mixed solution boiling and terpine resin are complete when molten, add the anhydrous AlCl of 21 grams again
3Catalyzer.Temperature is controlled at 80 to 85 ℃ of reactions 5 hours.Stop heating, cooling adds 110ml water in three-necked bottle.Continue to stir, to destroy the complex compound of chlorine, behind the several minutes, after adding the hydrochloric acid of 30ml36% again and stirring for some time, the product in the three-necked bottle is transferred in the beaker, standing demix is isolated the viscous fluid of upper strata brown-green, i.e. organic layer.With the saturated NaCl solution washing (100ml/ time) of heat, wash altogether 5 times, wash twice again with water, separate obtaining organic layer, use anhydrous Na
2SO
4Drying, the brown-green viscous fluid that obtains at last is exactly the pyrocatechol modified terpene resin.Raw material as coating.
Embodiment 2
Take by weighing the terpine resin of 200 grams, porphyrize, 20 gram pyrocatechols, add 1000ml three strength and answer in the bottle,, load onto spherical condensating tube and thermometer with the dissolving of 500ml toluene, heating and stir with electric power in electric mantle when mixed solution boiling and terpine resin are complete when molten, adds 32 gram catalyst A lCl again
3Temperature is controlled at 80 to 85 ℃ of reactions 4 hours.Stop heating, cooling adds 110ml water in three-necked bottle.Continue to stir, to destroy the complex compound of chlorine, behind the several minutes, after adding the HCL of 50ml 36% again and stirring for some time, the product in the three-necked bottle is transferred in the beaker, standing demix is isolated the viscous fluid of upper strata brown green, i.e. organic layer.Must not solution washing (100ml/ time) with the saturated NaCl of heat, wash altogether 3 times, wash twice again with water, separate obtaining organic layer, use anhydrous Na
2SO
4Drying, the brown-green viscous fluid that obtains at last is exactly the pyrocatechol modified terpene resin.The raw material of filming as coating.
Embodiment 3
100 kilograms of terpine resins are ground, be put in the reactor of whipping appts, add the pyrocatechol of pressing terpine resin part by weight 10-20%,, add catalyst A lCl with 1-3 gasoline dissolving doubly
3, content is 5～25%, and temperature is controlled at 80 to 85 ℃ of reactions 3-8 hour, cooling adds water and continues to stir, and with the complex compound of destruction chlorine, after adding HCl again and stirring for some time, standing demix, isolating the upper strata is organic layer.Saturated NaCl solution washing with heat washes twice again with water, separates to obtain organic layer, uses anhydrous Na
2SO
4Drying obtains the pyrocatechol modified terpene resin at last, can also can be used as the raw material of following coating as the raw material of filming of coating.
Embodiment 4
800 kilograms of terpine resins are ground, be put in the reactor of whipping appts, add the pyrocatechol of pressing terpine resin part by weight 10-20%, with 1-3 gasoline dissolving doubly, AlCl
3, content is 5～25%, and temperature is controlled at 80 to 85 ℃ of reactions 3-8 hour, cooling adds water and continues to stir, and with the complex compound of destruction chlorine, after adding HCL again and stirring for some time, standing demix, isolating the upper strata is organic layer.Saturated NaCl solution washing with heat washes twice again with water, separates to obtain organic layer, uses anhydrous Na
2SO
4Drying obtains the pyrocatechol modified terpene resin at last, can also can be used as the raw material of following coating as the raw material of filming of coating.
The pyrocatechol modified terpene resin of above-mentioned several embodiment is mixed with coating, the performance of coating is carried out following several test, testing method is as follows:
1, performance test is surveyed sticking power by GB GB1720-79; Survey the sticking power of filming with QFZ type Coating adhesion test instrument, check the syringe needle of adherometer before surveying earlier, should not change as sharp keen; During mensuration, model just is being placed on the testing table fixing, is making the tip of rotating the needle touch paint film, cycloid indentation standard map is long for about 7.5cm, has surveyed the taking-up model, consider to be worth doing with the lacquer that painting brush is removed on the cut, check the cut grading, mark 1,2 with cut on the model, 3, seven positions such as 4,5,6,7 grades.Correspondingly be divided into seven registrations.Check the paint film integrated degree at a position in order.Quadrille as a certain position is intact more than 70%, and it is intact then being decided to be this position.Intact as position 1 paint film, sticking power the best is decided to be one-level, and the like, seven grades is sticking power the best.
2, hardness test is surveyed hardness by GB GB1730-79; Survey the hardness of paint film with the QHQ type pencil scratch hardness instrument of filming.This instrument mainly contains pencil frame and testing table to be formed, the pencil frame with upright lean on to wait form testing table and keep 45 to spend angles constant.Testing table can be laterally, vertically move.With its fixing coating model, and model is moved towards the cut direction, the older generation just marks corresponding track in test piece by this.Use different pencils instead and mark different vestiges.The decidable hardness value of filming in view of the above.Plow five road vestiges successively with a certain hardness pencil, check five road vestiges, as have only the pencil that next time films in the plough way, then this one-level pencil hardness value is exactly the tested hardness of filming of representative.Otherwise the pencil that just changes another hardness is surveyed again.
3, surging force test is surveyed surging force by GB GB1732---79.Survey the surging force of lacquer with QCJ type paint film impactor.This is the impact paint film that utilizes weight to fall from eminence toward lower, to measure the shock strength of paint film.There is the controller screw that weight is fixed on the desired height in place, it highly has in the calibration and can read, pin the control screw, it gets rid of connection and things falls, the bump jumper bar, jumper bar acts on downwards on the sample board that is placed in advance on the pillow block, promote the weight body afterwards, take out the proof plate of analysing, to observe model japanning film test situation, paint film impacts moves the capital to another place with 1 kilogram weight hammering blow paint film, and the unlikely boundary height that has made damage is with centimetre expression.
4, petrol-resistance test, by international GB1734---79 survey petrol-resistance; By GB GB625---77 survey acid resistance; By GB GB629---77 survey alkali resistance.Exactly lamina membranacea is immersed in the chemical agent, checked once in per 24 hours, check phenomenons such as the paint film of lamina membranacea has or not loss of gloss, variable color, vesicle, spot, come off at every turn, whether qualified in the product standard regulation.
Claims (4)
1, a kind of synthetic method of pyrocatechol modified terpene resin, it is characterized in that: earlier terpine resin is ground, be put in the reactor of whipping appts, add the pyrocatechol of pressing terpine resin part by weight 10～20%, with 1～3 times dissolution with solvents, add anhydrous AlCl
3Catalyzer, content account for 5～25% of reaction-ure mixture, and temperature is controlled at 80 to 85 ℃ of reactions 3-8 hour, cooling, add water and continue to stir, add hydrochloric acid again and stir for some time standing demix, isolating the upper strata is organic phase, use the salt water washing, wash twice again with water, separate obtaining organic layer, drying obtains the pyrocatechol modified terpene resin at last.
2, the synthetic method of pyrocatechol modified terpene resin according to claim 1 is characterized in that: the solvent of dissolving terpine resin and pyrocatechol is selected in gasoline and benzene, toluene, kerosene, ethyl acetate, perhaps selects mixed solvent for use.
3, the synthetic method of pyrocatechol modified terpene resin according to claim 1 is characterized in that: the salt solution of washing organic phase process is the saturated NaCl solution of heat.
4, the synthetic method of pyrocatechol modified terpene resin according to claim 1 is characterized in that: the material of dry pyrocatechol modified terpene resin is an anhydrous Na
2SO
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012706 CN1249106C (en) | 2004-02-03 | 2004-02-03 | Process for synthesizing catechol modified terpene resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012706 CN1249106C (en) | 2004-02-03 | 2004-02-03 | Process for synthesizing catechol modified terpene resin |
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| Publication Number | Publication Date |
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| CN1557845A true CN1557845A (en) | 2004-12-29 |
| CN1249106C CN1249106C (en) | 2006-04-05 |
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| CN 200410012706 Expired - Fee Related CN1249106C (en) | 2004-02-03 | 2004-02-03 | Process for synthesizing catechol modified terpene resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009062146A2 (en) * | 2007-11-09 | 2009-05-14 | Northwestern University | Substrate-independent layer-by-layer assembly using catechol-functionalized polymers |
-
2004
- 2004-02-03 CN CN 200410012706 patent/CN1249106C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009062146A2 (en) * | 2007-11-09 | 2009-05-14 | Northwestern University | Substrate-independent layer-by-layer assembly using catechol-functionalized polymers |
| WO2009062146A3 (en) * | 2007-11-09 | 2010-01-28 | Northwestern University | Substrate-independent layer-by-layer assembly using catechol-functionalized polymers |
| US8293867B2 (en) | 2007-11-09 | 2012-10-23 | Northwestern University | Substrate-independent layer-by-layer assembly using catechol-functionalized polymers |
| US8551568B2 (en) * | 2007-11-09 | 2013-10-08 | Northwestern University | Substrate-independent layer-by-layer assembly using catechol-functionalized polymers |
| US8829154B2 (en) | 2007-11-09 | 2014-09-09 | Northwestern University | Substrate-independent layer-by-layer assembly using catechol-functionalized polymers |
| US9296843B2 (en) | 2007-11-09 | 2016-03-29 | Northwestern University | Substrate-independent layer-by-layer assembly using catechol-functionalized polymers |
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| Publication number | Publication date |
|---|---|
| CN1249106C (en) | 2006-04-05 |
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