CN103627324A - Preparation method of hydrogenated rosin without crystallization tendency - Google Patents
Preparation method of hydrogenated rosin without crystallization tendency Download PDFInfo
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- CN103627324A CN103627324A CN201310625511.8A CN201310625511A CN103627324A CN 103627324 A CN103627324 A CN 103627324A CN 201310625511 A CN201310625511 A CN 201310625511A CN 103627324 A CN103627324 A CN 103627324A
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Abstract
The invention discloses a preparation method of hydrogenated rosin without crystallization tendency. The method comprises the following steps: (1) dissolving a C5-C8 saturated alkane for existing hydrogenated rosin, wherein the weight ratio of the C5-C8 saturated alkane to the existing hydrogenated rosin is more than 1, agitating to sufficiently dissolve, stopping agitating when the dissolving balance is achieved; (2) keeping the solution of the step (1) at 0-25 DEG C, standing for 4-8 hours to sufficiently crystallize and separate out the hydrogenated rosin with crystallization tendency, filtering the crystallized hydrogenated rosin, separating filtrate by distillation to separate a solvent to obtain the hydrogenated rosin without crystallization tendency. The method is simple in process and the hydrogenated rosin which is free from crystallization tendency, low in ash content and high in stability can be obtained through the method. And meanwhile, the invention further discloses the hydrogenated rosin without crystallization tendency prepared by using the method, the hydrogenated rosin without crystallization tendency is oxidation resistant and ageing resistant, and can be widely applied to the fields of adhesive, electronic soldering flux, coating, printing ink, rubber and the like.
Description
Technical field
The present invention relates to a kind of preparation method of staybelite, especially a kind of preparation method without crystallization trend, low ash content, high stable staybelite.
Background technology
Rosin is renewable natural resource, China's pine tree aboundresources, and its rosin producing is the most important product of China's chemistry of forest product industry, is also mainstay industry.Rosin is because of its special molecular structure and performance, and be widely used in the industries such as coating, ink, tackiness agent, electronics, high speed development along with industry-by-industry technology, specification of quality to rosin and deep processed product thereof also improves constantly, anti-crystallization, ageing resistance become one of important quality index of rosin and deep processed product thereof, consistency is good, and without crystallization, ageing-resistant performance is good, has become the important factor that determines unit product price.
One of shortcoming of rosin is exactly that ageing resistance is poor, easily variable color.The reason of rosin variable color is: in rosin acid structure, have conjugated double bond oxygen uptake and variable color; The not existence of the coloring material such as strong polarity polyfunctional compound and variable color in Separation of Neutral thing in rosin.One for rosin the feature because of conjugated double bond oxygen uptake variable color, adopt two key modification technologies or light technology both at home and abroad, change the saturation ratio of conjugated double bond, and produce a series of modified rosin, wherein the most shallow with staybelite color, structure is the most stable, antioxidant good, fragility is little, Heat stability is good.Two existence for coloring materials such as strong polarity polyfunctional compounds in the neutrals in rosin, adopt distilation technology more.Rosin, under the condition of high vacuum, is removed neutrals, improve rosin color, but because abietic acid content in resin after purifying is higher, conjugated double bond content is relatively high, than the easier oxidation stain of common rosin, therefore generally directly do not use resin.
The another one shortcoming of rosin is exactly easy crystallization.CRYSTALLIZATION OF ROSIN is one of major issue affecting rosin quality, and crystallization rosin fusing point is higher, is difficult to saponification, has the trend of recrystallize in common solvent, can make sizing agent occur floss or small-particle precipitation in sizing agent, makes glue become opaque; In solder flux, occur floss when temperature (especially lower), postwelding is prone to local polymerization and reduces the transparency of film, and being difficult to saponification meeting affects its cleaning efficiency.Crystallization reduces the use value of rosin, and serious crystallization rosin should be processed as not being listed as level.
The fact being well known, various staybelite reaction process are basic identical, best hydrogenation scheme is in inert solvent, take active noble metals as catalyzer staybelite, such as platinum, palladium, iridium, rhodium, osmium, ruthenium, nickel, cobalt etc. under certain hydrogen pressure.The benefit that adopts noble metal catalyst is under lower temperature and lower hydrogen pressure, to realize hydrogenation.Yet, although there are these advantages, because exist sizable catalyst attrition in process, make to adopt precious metal catalyst hydrogenation process so uneconomical.Noble metal catalyst has a kind of tendency that forms colloid in solvent, and under this existence form, they cannot pass through filtering separation, and forms not recyclablely along with solvent is mixed together in staybelite, and causes and in staybelite, contains heavy metal.
Disclosed rosin hydrogenation process has several as follows:
U.S. Yi Jia factory, take wood rosin as raw material, adopting 5% palladium charcoal is catalyzer, under hydrogen pressure 250-350 kilogram of pressure/square centimeter, at 240-280 ℃, rosin heating melting is carried out to hydrogenation hydrogenation 4-20 hour, then, by toluene dissolution filter separating catalyst for the staybelite of preparation, redistillation is removed solvent toluene and is obtained staybelite, the method hydrogenation pressure conditional request is too high, and catalyst loss is large.
Mono-kind of patent CN98115885 makes raw material with dissolution with solvents rosin or rosin, and under catalyzer condition, through industrialization fixed bed continuous hydrogenation, and then filtering separation obtains the staybelite manufacture method of staybelite.The method has been introduced dissolution with solvents rosin, effectively reduce rosin melt viscosity, make hydrogenation reaction pressure require to reduce, reduce production cost and risk, but still just adopt traditional filter method separating catalyst, cannot reclaim with liquid gum state and be dissolved in the noble metal catalyst in solvent.
The pale rosin that patent CN102070988 be take after rosin purification is hydrogenating materials, dissolution with solvents wiring solution-forming, under catalyzer condition, through industrialization fixed bed continuous hydrogenation or suspension floating bed reactor shortening intermittently, and then filtration, fractionation by distillation obtain the manufacture method of water-white hydrogenated rosin.The method, by refining purification rosin, although improved the color grade of staybelite, still just adopts traditional filter method separating catalyst, and the number of dropouts of noble metal catalyst is very large.
The water-white hydrogenated rosin of selling on the market at present, it adopts traditional precious metal palladium charcoal catalytic hydrogenation production technique to produce staybelite, later stage is through the molecular distillation of absolute pressure (0.400-4.00) kPa, collecting recovered temperature is 195-250 ℃ of fraction, after condensation, obtain the water-white hydrogenated rosin that bullion content is low, but the method there is the staybelite part of crystallization trend in cannot separated staybelite.
Adopt above method to produce staybelite, mainly contain following shortcoming: the one, while producing, pressure is large, high to equipment requirements; The 2nd, noble metal catalyst number of dropouts is large, and Financial cost is high, contains the noble metal of loss in product, affects the later stage application safety of product; The 3rd, there is crystallization tendency in the staybelite of preparation, the application of product in some special adhesive is also restricted, and particularly the application in advanced electronic soldering flux is restricted.
Summary of the invention
Thereby the object of the invention is to overcome above-mentioned the deficiencies in the prior art part and a kind of noble metal catalyst that can isolate glial state from staybelite be provided and have the staybelite of crystallization trend to obtain the method without crystallization trend staybelite; Meanwhile, the present invention also provides the staybelite without crystallization trend that adopts described method to prepare.
For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method without crystallization trend staybelite, comprises the following steps:
(1) existing staybelite is dissolved with C5-C8 saturated alkane, wherein the weight ratio of C5-C8 saturated alkane and existing staybelite is greater than 1, stirs fully and dissolves, and stops stirring after reaching dissolution equilibrium;
(2) solution of step (1) is remained on to 0-25 ℃, standing 4-8 hour, separates out the staybelite sufficient crystallising of crystallization trend, filters out the staybelite of crystallization, by after filtrate fractionation by distillation solvent, obtains the staybelite without crystallization trend.
Present inventor has found a uniqueness but fairly simple preparation technology through large quantity research, can effectively from staybelite, isolate the noble metal catalyst and the staybelite that has crystallization trend of glial state, in described step (2), have in the process that the staybelite sufficient crystallising of crystallization trend separates out, colloid state noble metal catalyst also adsorbs in the staybelite that is wrapped in crystallization, staybelite with crystallization is filtered out, thereby obtain without crystallization trend, ash oontent is low, the staybelite that antioxidative stabilizer is good, the softening temperature of the resulting staybelite without crystallization trend is 62-72 ℃, acid number is 160～165mgKOH/g, color is less than Ghana's look No. 6.
As the preparation method's without crystallization trend staybelite of the present invention preferred implementation, in described step (1), the mass ratio of C5-C8 saturated alkane and existing staybelite is 1～20; As the preparation method's without crystallization trend staybelite of the present invention more preferably embodiment, in described step (1), the mass ratio of C5-C8 saturated alkane and existing staybelite is 1～5.The mass ratio of C5-C8 saturated alkane and existing staybelite is can not be lower than 1, if lower than 1, and, the easy Precipitation of hydroabietic acid, not can not get pure crystallization hydrogen sylvic acid substantially.Preferably the mass ratio of C5-C8 saturated alkane and existing staybelite is not higher than 5, owing to there being crystallization trend hydroabietic acid to be slightly soluble in hydro carbons, the increase of hydrocarbon usage quantity, there is the acid recovery of crystallization staybelite few, easily cause without crystallization staybelite purity inadequate, and hydrocarbon usage quantity increases, finally distilling energy consumption increases.
As the preparation method's without crystallization trend staybelite of the present invention preferred implementation, described method is further comprising the steps:
(3) by the crystallization staybelite filtering out in step (2), in with crystallization staybelite quality 3-8 C5-C8 saturated alkane solvent doubly, reflux is dissolved, then add the gac backflow of crystallization staybelite quality 5～10% to adsorb 30 minutes, filtered and recycled gac, reduce solution temperature to-10～35 ℃, crystallization crystallization staybelite, the dry staybelite that obtains crystallization trend, the gac reclaiming reclaims noble metal catalyst by burning.
In the method for the invention, further comprise step described above (3), the noble metal catalyst in the crystallization staybelite filtering out is removed in recovery, thereby can be by the effective Separation and Recovery of the noble metal catalyst in staybelite, and can obtain two kinds of new staybelites simultaneously, be a staybelite that has crystallization trend, another kind is the staybelite without crystallization trend described above.Resulting to have the softening temperature of the staybelite of crystallization trend be 85～100 ℃, and acid number is 180～185mgKOH/g, and color is less than Ghana's look No. 6.Step (3) gained has the staybelite of crystallization trend, and its content is 15～25% of raw material staybelite (being existing staybelite) weight.
As the preparation method's without crystallization trend staybelite of the present invention preferred implementation, described gac is wood activated charcoal or cocoanut active charcoal.Preparation method's without crystallization trend staybelite the most of the present invention more preferably embodiment, described gac is selected the cocoanut active charcoal that specific surface area is large, intensity is higher, can better adsorb recovery noble metal catalyst.
As the preparation method's without crystallization trend staybelite of the present invention preferred implementation, the staybelite without crystallization trend obtaining in described step (2), adopts molecular distillation process for refining, obtains water-white without the staybelite of crystallization trend.
Preferred implementation as the preparation method without crystallization trend staybelite of the present invention, existing staybelite in described step (1) is directly prepared from purchased from market or employing following methods: take common rosin or rosin derivative as raw material, with solvent oil, make solvent, at 60～180 ℃, being made into mass ratio is 20～60% solution, solution is added in hydrogenator, under the effect of hydrogenating reduction catalyzer, carry out hydrogenation reaction, product removes by filter hydrogenating reduction catalyzer, distillation, except desolventizing, obtains existing staybelite.When described existing staybelite is during directly purchased from market, preferably, described existing staybelite selects to meet the common staybelite of national standard, highly hydrogenated rosin; More preferably, described existing staybelite selects to meet the highly hydrogenated rosin of national standard.
As the preparation method's without crystallization trend staybelite of the present invention preferred implementation, described common rosin is a kind of in gum resin, wood rosin, toll oil rosin; Described rosin derivative is resin.
As the preparation method's without crystallization trend staybelite of the present invention preferred implementation, in the preparation process of described existing staybelite, solvent oil is at least one in C5-C8 saturated alkane, pinane, 120# solvent oil, 200# solvent oil; As the preparation method's without crystallization trend staybelite of the present invention more preferably embodiment, described solvent oil is at least one in hexane, heptane, octane, pinane.Hexane, heptane, octane are liquid light hydrocarbon at normal pressure, and in heating, pressurization situation, because the boiling point of hexane, heptane, octane is 68.7-125.6 degree, easily gasification, increased gas-liquid turbulent flow touch opportunity in hydriding reactor, more utilize rosin hydrogenation, when improving hydrogenation efficiency, reduced hydrogenation pressure requirement.Pinane is that the turps hydrogenation distilling in rosin production process makes, and for rosin production enterprise, raw material is taken conveniently, has avoided the trouble of the links such as solvent oil buying, transportation.
As the preparation method's without crystallization trend staybelite of the present invention preferred implementation, described hydrogenating reduction catalyzer is at least one in platinum, palladium, iridium, rhodium, osmium, ruthenium, nickel, cobalt; As the preparation method's without crystallization trend staybelite of the present invention more preferably embodiment, described hydrogenating reduction catalyzer is at least one in palladium charcoal, Raney's nickel.Platinum, palladium, nickel carried catalyst and skeleton nickel etc., for alkynes, selective hydrogenation of diolefin as, oil hydrogenation etc., most for saturated hydrogenation.It both can add two keys also can add carbonyl, rosin great majority are unsaturated polyester acid, its hydrogenation to be generated to saturated tree resin acid, the catalytic efficiencies that adopt high more, the platinum of Heat stability is good, palladium, nickel, because platinum price is more expensive, therefore more preferably adopt relatively cheap, good dispersity palladium carbon, Raney's nickel.
Simultaneously, the present invention also provides the staybelite that adopts the staybelite without crystallization trend that method prepares as mentioned above and have crystallization trend, the softening temperature of the described staybelite without crystallization trend is 62-72 ℃, and acid number is 160～165mgKOH/g, and color is less than Ghana's look No. 6; Described to have the softening temperature of the staybelite of crystallization trend be 85～100 ℃, and acid number is 180～185mgKOH/g, and color is less than Ghana's look No. 6.Staybelite without crystallization trend of the present invention is compared with existing staybelite, the present invention is forming without crystallization trend isomer of a large amount of not containing hydrogenated derivatives and neutrals without the staybelite of crystallization trend, resistance to oxidation is aging more, can within a very long time, keep the initial viscosity of this rosin, therefore Application Areas is extensive, can be applicable to the fields such as tackiness agent, electronics soldering flux, coating, ink, rubber.The staybelite that has crystallization trend of the present invention, can be with phosphorus trichloride or sulfur oxychloride process for producing light color staybelite chlorinated derivatives.
Preparation method without crystallization trend staybelite of the present invention, technique is simple, can effectively from existing staybelite, isolate the noble metal catalyst and the staybelite that has crystallization trend of glial state, isolated noble metal catalyst with the staybelite that has a crystallization trend through follow-up further separated, thereby noble metal catalyst is reclaimed and obtains a kind of new material: the staybelite that has crystallization trend, the method of the invention efficient recovery the solvability colloid noble metal catalyst running off in staybelite production process in solvent, greatly reduce in staybelite noble metal catalyst residual simultaneously, there is good economic benefit.
Adopt that the method for the invention prepares without crystallization trend, low ash content, high stable staybelite, with respect to existing staybelite, the present invention is forming without crystallization trend isomer of a large amount of not containing hydrogenated derivatives and neutrals without the staybelite of crystallization trend, resistance to oxidation is aging more, can within a very long time, keep the initial viscosity of this rosin, therefore Application Areas is extensive, can be applicable to the fields such as tackiness agent, electronics soldering flux, coating, ink, rubber.In addition, by isolated noble metal catalyst and the staybelite that has a crystallization trend through follow-up further separated after, a kind of new material obtaining: there is the staybelite of crystallization trend, can be with phosphorus trichloride or sulfur oxychloride process for producing light color staybelite chlorinated derivatives.
Embodiment
For the object, technical solutions and advantages of the present invention are better described, below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The present invention is without a kind of embodiment of the preparation method of crystallization trend staybelite, and the present embodiment said method comprising the steps of:
(1) in the autoclave that is 2L toward volume, add 400 grams of superfine rosin (acid number 169mgKOH/g, 77 ℃ of softening temperatures, Ghana look 5+), add normal hexane, be adjusted to rosin content at 30%-50%, by the 0.3-1% of rosin weight, add powdery 5% palladium carbon catalyst (moisture 50%), vacuumize, with air in nitrogen replacement still 2-3 time, be filled with again in hydrogen exchange still nitrogen 2-3 time, post-heating is to 90-120 ℃ of dissolving, regulate hydrogen pressure in still, start the heating of autoclave, stirring system, continuous hydrogen make-up, keep hydrogen pressure at 50-100 kilogram of pressure/square centimeter, be warmed up to 180-240 ℃, until no longer declining, hydrogen pressure finishes reaction, reaction times 1-4 hour, stop heating, reduce the temperature to 40 ℃, separate press filtration, filtrate is transferred in four-hole boiling flask, normal hexane and staybelite 396g(dihydro sylvic acid 67.83% are isolated in underpressure distillation, tetrahydrochysene sylvic acid 25.04%, dehydroabietic acid 5.28%, abietic acid 1.85%, in rosin amount ash content >0.05%, in rosin amount palladium content >5.0ppm),
(2) between 30～40 ℃, with 390 grams of the 390 grams of abundant stirring and dissolving gained of normal hexane staybelites, , after reaching dissolution equilibrium, stop stirring, solution is remained on to 5-10 ℃, standing 4-8 hour, the staybelite sufficient crystallising of crystallization trend is separated out, colloid state precious metal also adsorbs and is wrapped in crystallization rosin, decantation goes out 72 grams of (acid number 182mgKOH/g of staybelite of crystallization, 91.5 ℃ of softening temperatures, Ghana's look 3, dihydro sylvic acid 71.5%, tetrahydrochysene sylvic acid 23.12%, dehydroabietic acid 4.16%, abietic acid 1.22%), by after filtrate fractionation by distillation solvent, obtain without 325 grams of (acid number 165mgKOH/g of crystallization trend staybelite, 67 ℃ of softening temperatures, Ghana's look is 3+, dihydro sylvic acid 66.94%, tetrahydrochysene sylvic acid 25.71%, dehydroabietic acid 5.43%, abietic acid 1.92%, ash content 0.00%, palladium content <0.5ppm), by obtain without crystallization trend staybelite molecular distillation process for refining in addition, can obtain water-white without crystallization trend, low ash content, high stable staybelite.
Further, described in the present embodiment, method can also comprise the following steps:
(3) by 50 grams of the crystallization staybelites filtering out, add in reflux in crystallization rosin quality 3-8 normal hexane solvent doubly and dissolve, after add again the absorption 30 minutes that refluxes of the cocoanut active charcoal of crystallization rosin quality 5%-10%, filtered and recycled gac, reduce solution temperature to 0-35 ℃, crystallization crystallization filtration drying dries up and obtains 46 grams of pure crystallization staybelites, and resulting recovered carbon reclaims precious metal palladium by burning.
Embodiment 2
The present invention is without a kind of embodiment of the preparation method of crystallization trend staybelite, and the present embodiment said method comprising the steps of:
(1) in the autoclave that is 2L toward volume, add 400 grams of superfine rosin (acid number 169mgKOH/g, 77 ℃ of softening temperatures, being dissolved in Ghana's look that toluene is made into 50% solution is 5+), add pinane, be adjusted to rosin content at 30%-70%, by the 0.3-1% of rosin weight, add powdery 5% palladium carbon catalyst (moisture 50%), vacuumize, with air in nitrogen replacement still 2 times, be filled with again in hydrogen exchange still nitrogen 2-3 time, post-heating is to 100-160 ℃ of dissolving, regulate hydrogen pressure in still, start the heating of autoclave, stirring system, continuous hydrogen make-up, keep hydrogen pressure at 80-160 kilogram of pressure/square centimeter, be warmed up to 180-260 ℃, until no longer declining, hydrogen pressure finishes reaction, reaction times 1-4 hour, stop heating, reduce the temperature to 100 ℃, separate press filtration, filtrate is transferred in four-hole boiling flask, pinane and 398 grams of staybelites (acid number 164.7(mgKOH/g) are isolated in underpressure distillation, 77.5 ℃ of softening temperatures, Ghana's look is 3+, dihydro sylvic acid 50.0%, tetrahydrochysene sylvic acid 43.41%, dehydroabietic acid 5.63%, abietic acid 0.96%, in rosin amount ash content >0.04%, in rosin amount palladium content >5.0ppm).
(2) between 30-40 ℃, with 390 grams of the 780 grams of abundant stirring and dissolving gained of normal heptane staybelites, after reaching dissolution equilibrium, stop stirring, solution is remained on to 0-5 ℃, standing 4-8 hour, the staybelite sufficient crystallising of crystallization trend is separated out, colloid state precious metal also adsorbs and is wrapped in crystallization rosin, decantation goes out 76 grams of (acid number 184.5mgKOH/g of staybelite of crystallization, 93.5 ℃ of softening temperatures, Ghana's look is 4, dihydro sylvic acid 57.73%, tetrahydrochysene sylvic acid 36.66%, dehydroabietic acid 4.86%, abietic acid 0.75%), by after filtrate fractionation by distillation solvent, obtain without 312 grams of (acid number 164mgKOH/g of crystallization trend staybelite, 66 ℃ of softening temperatures, being dissolved in Ghana's look that toluene is made into 50% solution is 5+, dihydro sylvic acid 47.39%, tetrahydrochysene sylvic acid 45.83%, dehydroabietic acid 5.79%, abietic acid 0.99%, ash 0.00%, palladium content <0.5ppm).Gained, without crystallization trend staybelite molecular distillation process for refining in addition, is collected to 185-250 ℃ of cut, and condensation can obtain water-white without crystallization trend, low ash content, high stable staybelite.
Further, described in the present embodiment, method can also comprise the following steps:
(3) by 60 grams of the crystallization staybelites filtering out, add in reflux in crystallization rosin quality 3-8 normal heptane solvent doubly and dissolve, after add again the absorption 30 minutes that refluxes of the cocoanut active charcoal of crystallization rosin quality 5%-10%, filtered and recycled gac, reduce arrive-5-25 ℃ of solution temperature, crystallization crystallization filtration drying dries up and obtains pure crystallization staybelite 57g, and resulting recovered carbon reclaims precious metal palladium by burning.
Embodiment 3
The present invention is without a kind of embodiment of the preparation method of crystallization trend staybelite, and the present embodiment said method comprising the steps of:
(1) in the autoclave that is 2L toward volume, add 300 grams of superfine rosins (acid number 169(mgKOH/g), 77 ℃ of softening temperatures, Ghana look 4-), add octane, be adjusted to rosin content at 20%-50%, press the powdery Raney's nickel of the 5%-10% of rosin weight, vacuumize, with air in nitrogen replacement still 2 times, be filled with again in hydrogen exchange still nitrogen 2-3 time, post-heating is to 90-120 ℃ of dissolving, regulate hydrogen pressure in still, start the heating of autoclave, stirring system, continuous hydrogen make-up, keep hydrogen pressure at 100-150 kilogram of pressure/square centimeter, be warmed up to 160-240 ℃, until no longer declining, hydrogen pressure finishes reaction, reaction times 1-4 hour, stop heating, reduce the temperature to 40 ℃, separate press filtration, filtrate is transferred in four-hole boiling flask, octane and staybelite 297g(dihydro sylvic acid 36.87% are isolated in underpressure distillation, tetrahydrochysene sylvic acid 56.88%, dehydroabietic acid 5.66%, abietic acid 0.31%, in rosin amount ash content >0.05%, in rosin amount nickel content >5.0ppm),
(2) between 30～40 ℃, with the abundant stirring and dissolving gained of 5600g octane staybelite 280g, after reaching dissolution equilibrium, stop stirring, solution is remained on to 0-5 ℃, standing 4-8 hour, the staybelite sufficient crystallising of crystallization trend is separated out, colloid state precious metal also adsorbs and is wrapped in crystallization rosin, decantation goes out 66 grams of (86.5 ℃ of softening temperatures of staybelite of crystallization, acid number 180.5mgKOH/g, Ghana's look is 4, dihydro sylvic acid 43.83%, tetrahydrochysene sylvic acid 51.58%, dehydroabietic acid 4.34%, abietic acid 0.25%), by after filtrate fractionation by distillation solvent, obtain without 225 grams of crystallization trend staybelites (62 ℃ of softening temperatures, acid number 160.5mgKOH/g, dihydro sylvic acid 33.9%, tetrahydrochysene sylvic acid 59.93%, dehydroabietic acid 5.84%, abietic acid 0.33%, Ghana's look is 4+, ash content 0.00%, nickel content <0.5ppm).
Further, described in the present embodiment, method can also comprise the following steps:
(3) by 55 grams of the crystallization staybelites filtering out, add in reflux in crystallization rosin quality 3-8 octane solvent doubly and dissolve, after add again the absorption 30 minutes that refluxes of the cocoanut active charcoal of crystallization rosin quality 5%-10%, filtered and recycled gac, reduce arrive-10-10 ℃ of solution temperature, crystallization crystallization filtration drying dries up and obtains 52.5 grams of pure crystallization staybelites, and resulting recovered carbon reclaims precious metal nickel by burning.
Embodiment 4
The present invention is without a kind of embodiment of the preparation method of crystallization trend staybelite, and the present embodiment said method comprising the steps of:
(1) in the four-hole vial that is 2L toward volume, add 300 grams of common staybelites of commercially available superfine (acid number 165.9(mgKOH/g), 77 ℃ of softening temperatures, Ghana's look is 5-, dihydro sylvic acid 71.22%, tetrahydrochysene sylvic acid 20.82%, dehydroabietic acid 6.14%, abietic acid 1.62%), add 1500 grams of hexanaphthenes, fully stir, after reaching dissolution equilibrium, stop stirring;
(2) solution of step (1) is kept approaching 0 ℃, standing 8 hours, the staybelite sufficient crystallising of crystallization trend is separated out, decantation goes out 73 grams of (95 ℃ of softening temperatures of staybelite of crystallization, acid number 185mgKOH/g, Ghana's look is 5, dihydro sylvic acid 74.97%, tetrahydrochysene sylvic acid 18.86%, dehydroabietic acid 4.92%, abietic acid 1.08%), by after filtrate fractionation by distillation solvent, obtain without 222 grams of crystallization trend staybelites (67 ℃ of softening temperatures, acid number 161mgKOH/g, Ghana's look is 5-, dihydro sylvic acid 70.53%, tetrahydrochysene sylvic acid 22.04%, dehydroabietic acid 5.9.4%, abietic acid 1.23%, ash content 0.00%, palladium content <0.5ppm).
Further, described in the present embodiment, method can also comprise the following steps:
(3) by 65 grams of the crystallization staybelites filtering out, add in reflux in crystallization rosin quality 3-8 normal hexane solvent doubly and dissolve, after add again the absorption 30 minutes that refluxes of the cocoanut active charcoal of crystallization rosin quality 5%-10%, filtered and recycled gac, reduce arrive-5-30 ℃ of solution temperature, crystallization crystallization filtration drying dries up and obtains 62.5 grams of pure crystallization staybelites, and resulting recovered carbon reclaims precious metal palladium by burning.
Embodiment 5
The present invention is without a kind of embodiment of the preparation method of crystallization trend staybelite, and the present embodiment said method comprising the steps of:
(1) in the four-hole vial that is 2L toward volume, add the 500 grams of highly hydrogenated rosin of commercially available superfine (acid number 165mgKOH/g, 78 ℃ of softening temperatures, Ghana's look 4, dihydro sylvic acid 38.02%, tetrahydrochysene sylvic acid 57.07%, dehydroabietic acid 4.45%, abietic acid 0.46%), add 1000 grams of octanes, fully stir, after reaching dissolution equilibrium, stop stirring;
(2) solution of step (1) is kept approaching 25 ℃, standing 4 hours, the staybelite sufficient crystallising of crystallization trend is separated out, decantation goes out 75 grams of (acid number 181mgKOH/g of staybelite of crystallization, 90.5 ℃ of softening temperatures, Ghana's look is 4+, dihydro sylvic acid 44.94%, tetrahydrochysene sylvic acid 51.24%, dehydroabietic acid 3.50%, abietic acid 0.32%), by after filtrate fractionation by distillation solvent, obtain without 420 grams of (acid number 162mgKOH/g of crystallization trend staybelite, 65 ℃ of softening temperatures, Ghana's look 5, dihydro sylvic acid 34.19%, tetrahydrochysene sylvic acid 60.67%, dehydroabietic acid 4.64%, abietic acid 0.49%, ash content 0.00%, palladium content <0.5ppm).
Further, described in the present embodiment, method can also comprise the following steps:
(3) by 65 grams of the crystallization staybelites filtering out, add in reflux in crystallization rosin quality 3-8 normal hexane solvent doubly and dissolve, after add again the absorption 30 minutes that refluxes of the cocoanut active charcoal of crystallization rosin quality 5%-10%, filtered and recycled gac, reduce solution temperature to 0-20 ℃, crystallization crystallization filtration drying dries up and obtains 62.5 grams of pure crystallization staybelites, and resulting recovered carbon reclaims precious metal palladium by burning.
From above embodiment, find out, by the present invention is separating obtained, without crystallization trend staybelite, compare with raw material staybelite, tetrahydrochysene sylvic acid content improves, ash content reduces, bullion content greatly reduces.
Owing to comparing with raw material staybelite without crystallization trend staybelite, tetrahydrochysene sylvic acid content improves, further improved staybelite structure saturation ratio, improve anti-oxidant aging ability, simultaneously because staybelite of the present invention is without crystallization trend, make without crystallization trend staybelite and macromolecular elastomer, to there is better consistency with the present invention, and can keep the original viscosity of material for a long time.What therefore the present invention prepared can be widely used in adhesive area without crystallization trend staybelite.
Owing to comparing with raw material staybelite without crystallization trend staybelite, ash content reduces, bullion content greatly reduces, and anti-oxidant aging stability improves simultaneously, makes this staybelite more be applicable to being applied to advanced electronic soldering flux.Efficient recovery noble metal catalyst of the present invention, has significant economic benefit.
Last institute should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although the present invention is explained in detail with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. without a preparation method for crystallization trend staybelite, it is characterized in that, comprise the following steps:
(1) existing staybelite is dissolved with C5-C8 saturated alkane, wherein the weight ratio of C5-C8 saturated alkane and existing staybelite is greater than 1, stirs fully and dissolves, and stops stirring after reaching dissolution equilibrium;
(2) solution of step (1) is remained on to 0-25 ℃, standing 4-8 hour, separates out the staybelite sufficient crystallising of crystallization trend, filters out the staybelite of crystallization, by after filtrate fractionation by distillation solvent, obtains the staybelite without crystallization trend.
2. the preparation method without crystallization trend staybelite as claimed in claim 1, is characterized in that, in described step (1), the mass ratio of C5-C8 saturated alkane and existing staybelite is 1～20; Preferably, in described step (1), the mass ratio of C5-C8 saturated alkane and existing staybelite is 1～5.
3. the preparation method without crystallization trend staybelite as claimed in claim 1, is characterized in that, described method is further comprising the steps:
(3) by the crystallization staybelite filtering out in step (2), in with crystallization staybelite quality 3-8 C5-C8 saturated alkane solvent doubly, reflux is dissolved, then add the gac backflow of crystallization staybelite quality 5～10% to adsorb 30 minutes, filtered and recycled gac, reduce solution temperature to-10～35 ℃, crystallization crystallization staybelite, the dry staybelite that obtains crystallization trend, the gac reclaiming reclaims noble metal catalyst by burning.
4. the preparation method without crystallization trend staybelite as claimed in claim 3, is characterized in that, described gac is wood activated charcoal or cocoanut active charcoal.
5. the preparation method without crystallization trend staybelite as claimed in claim 1, is characterized in that, the staybelite without crystallization trend obtaining in described step (2) adopts molecular distillation process for refining, obtains water-white without the staybelite of crystallization trend.
6. the preparation method without crystallization trend staybelite as described in as arbitrary in claim 1 to 5, it is characterized in that, existing staybelite in described step (1) is directly prepared from purchased from market or employing following methods: take common rosin or rosin derivative as raw material, with solvent oil, make solvent, at 60～180 ℃, being made into mass ratio is 20～60% solution, solution is added in hydrogenator, under the effect of hydrogenating reduction catalyzer, carry out hydrogenation reaction, product removes by filter hydrogenating reduction catalyzer, distillation, except desolventizing, obtains existing staybelite.
7. the preparation method without crystallization trend staybelite as claimed in claim 6, is characterized in that, described common rosin is a kind of in gum resin, wood rosin, toll oil rosin; Described rosin derivative is resin.
8. the preparation method without crystallization trend staybelite as claimed in claim 6, is characterized in that, in the preparation process of described existing staybelite, solvent oil is at least one in C5-C8 saturated alkane, pinane, 120# solvent oil, 200# solvent oil; Preferably, described solvent oil is at least one in hexane, heptane, octane, pinane.
9. the preparation method without crystallization trend staybelite as claimed in claim 6, is characterized in that, described hydrogenating reduction catalyzer is at least one in platinum, palladium, iridium, rhodium, osmium, ruthenium, nickel, cobalt; Preferably, described hydrogenating reduction catalyzer is at least one in palladium charcoal, Raney's nickel.
An employing as arbitrary in claim 1-9 as described in the staybelite without crystallization trend for preparing of method and have the staybelite of crystallization trend, it is characterized in that, the softening temperature of the described staybelite without crystallization trend is 62-72 ℃, acid number is 160～165mgKOH/g, and color is less than Ghana's look No. 6; Described to have the softening temperature of the staybelite of crystallization trend be 85～100 ℃, and acid number is 180～185mgKOH/g, and color is less than Ghana's look No. 6.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194638A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Method for preparing anti-crystallization rosin |
| CN104194639A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Preparation method of anti-crystallization disproportionated rosin |
| CN108978080A (en) * | 2018-08-08 | 2018-12-11 | 山东奇士登润滑科技有限公司 | High temperature rosin activity oil and its manufacturing method |
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| JPH06279734A (en) * | 1993-03-26 | 1994-10-04 | Ryutaro Kinoshita | Production of hydrogenated rosin |
| CN1245192A (en) * | 1998-08-13 | 2000-02-23 | 广西壮族自治区苍梧县松脂厂 | Process for preparing hydrogenated rosin |
| CN102212314A (en) * | 2010-04-02 | 2011-10-12 | 盘锦和运新材料有限公司 | Method for preparing water-white highly-hydrogenated rosin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06279734A (en) * | 1993-03-26 | 1994-10-04 | Ryutaro Kinoshita | Production of hydrogenated rosin |
| CN1245192A (en) * | 1998-08-13 | 2000-02-23 | 广西壮族自治区苍梧县松脂厂 | Process for preparing hydrogenated rosin |
| CN102212314A (en) * | 2010-04-02 | 2011-10-12 | 盘锦和运新材料有限公司 | Method for preparing water-white highly-hydrogenated rosin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194638A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Method for preparing anti-crystallization rosin |
| CN104194639A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Preparation method of anti-crystallization disproportionated rosin |
| CN104194639B (en) * | 2014-07-25 | 2016-01-27 | 广西梧州松脂股份有限公司 | The preparation method of the brilliant nilox resin of resistive connection |
| CN104194638B (en) * | 2014-07-25 | 2016-01-27 | 广西梧州松脂股份有限公司 | The preparation method of the brilliant rosin of resistive connection |
| CN108978080A (en) * | 2018-08-08 | 2018-12-11 | 山东奇士登润滑科技有限公司 | High temperature rosin activity oil and its manufacturing method |
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| CN103627324B (en) | 2015-09-09 |
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Address after: 526238 South Zhenggang Bridge, Yingbin Avenue, Zhaoqing High-tech Zone, Guangdong Province Co-patentee after: Puer Kemao Forest Chemical Products Co., Ltd. Patentee after: Guangdong Komo Co., Ltd. Co-patentee after: Hunan Kemao Forest Chemical Co., Ltd. Address before: 526238 South Zhenggang Bridge, Yingbin Avenue, Zhaoqing High-tech Zone, Guangdong Province Co-patentee before: Puer Kemao Forest Chemical Products Co., Ltd. Patentee before: Guangdong Komo Co., Ltd. Co-patentee before: HUNAN KOMO FOREST CHEMICAL CO., LTD. |
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