CN102977230A - Method for removing hydrogenation catalyst in polymer solution - Google Patents
Method for removing hydrogenation catalyst in polymer solution Download PDFInfo
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- CN102977230A CN102977230A CN2011102593811A CN201110259381A CN102977230A CN 102977230 A CN102977230 A CN 102977230A CN 2011102593811 A CN2011102593811 A CN 2011102593811A CN 201110259381 A CN201110259381 A CN 201110259381A CN 102977230 A CN102977230 A CN 102977230A
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Abstract
The invention provides a method for removing a hydrogenation catalyst in a polymer solution. The polymer solution contains a polymer and a hydrogenation catalyst. The hydrogenation catalyst contains a trialkylaluminium co-catalyst and a VIII metal compound and/or a complex main catalyst. The method comprises the following steps that 1, water and silicate powder or particles contact with the polymer solution under airtight conditions to form precipitates; 2, the precipitates are separated out from the mixture obtained by the step 1, wherein based on the weight of the polymer solution, an addition ratio of the water is in a range of 0.01 to 2wt% and an addition ratio of the silicate powder or particles is in a range of 0.05 to 2wt%. The method can obviously reduce hydrogenation catalyst content of the treated polymer solution, does not produce the pollution on the polymer solution in a reaction of removing the hydrogenation catalyst in the polymer solution, and has a simple and low-energy consumption catalyst-containing precipitate separation process.
Description
Technical field
The present invention relates to a kind of method of removing hydrogenation catalyst in the polymers soln.
Background technology
The heat of unsaturated polymer, oxidative stability and ageing resistance are relatively poor, and therefore the normal method of hydrogenation that adopts makes the unsaturated link(age) of polymkeric substance saturated, thereby increases its environmental stability, and makes it have good thermostability.Hydrogenation of polymer carries out in the presence of heavy metal catalyst usually, and catalyst system therefor is the organic compound of the periodic table of elements VIIIB family metals such as Fe, Co, Ni and/or Pd, and organoaluminum or organolithium compound.These metal catalysts are the existence of transition-metal catalyst especially, not only make polymkeric substance with color, limit its use range, main is can accelerate the degraded of polymkeric substance or crosslinked, therefore behind hydrogenation of polymer, must remove wherein remaining a small amount of catalyzer, make polymkeric substance can anti-marquis, heat-resisting oxidation, ageing-resistant.In the prior art, require usually that residual transition metals content just can not cause detrimentally affect to the use properties of product less than 10ppm in the polymkeric substance.
US5,089,541 disclose a kind of method that removes hydrogenation catalyst in the polymers soln, the polymkeric substance that contains hydrogenation catalyst needs fully to contact with molecular oxygen, hydrogenation post polymerization thing solution after the oxidation contacts with gac again, and the content of group VIII metal can be less than 5ppm in the polymers soln that obtains.In this invention, used gac must be used with molecular oxygen, thereby with the cohesion that promotes nickel the suspended solid of formation is separated quickly from polymers soln.In this invention, the hydrogenation polymers soln must be with the abundant oxidation of molecular oxygen, and oxidization time is longer, also will be with a large amount of gacs, and the duration of contact of gac and polymers soln is long, and efficient is low, is not suitable for industrial amplification.
US4,595,749 disclose the method for removing the residual metal catalyzer a kind of hydrogenation post polymerization thing solution after unsaturated polymer hydrogenation, the method adopts oxygenant and dicarboxylic acid to remove residual metal catalyzer in the hydrogenation polymers soln, and dicarboxylic acid need to use carbonatoms to be less than 4 lower aliphatic alcohols or toluene and make solvent.When the method adopts lower aliphatic alcohols to make the dicarboxylic acid solvent, because it is approaching with the polymer solvent boiling point, make difficult solvent recovery; When making the dicarboxylic acid solvent with toluene, because dicarboxylic acid solvability in toluene is very poor, the toluene aequum is larger, and it is higher to reclaim energy consumption.
US5,281,696 disclose a kind of method that contacts separating catalyst residue from polymers soln by water and trialkylaluminium with the polymkeric substance that contains group VIII metal hydrogenation catalyzer.In the polymer product that reclaims by the method, the residual quantity of group VIII metal is less than 5ppm.The mixing that the method relates to can be finished in agitator or online static mixer, after mixing by filter, centrifugal or sedimentation removes hydrogenation catalyst.Yet the method needs a large amount of extra expensive aluminum alkyls and a certain amount of water of adding, and the aluminum alkyls that wherein adds and the mol ratio of group VIII metal are up to 20-160, and raw materials consumption is many; And catalyst residue disengaging time from polymers soln is long, and separation efficiency is not very high, is not suitable for industry and amplifies.
USH1303 discloses a kind of method that a small amount of water removes polymer hydrogenating catalyst that adds, although this method can effectively be removed the hydrogenation catalyst in the polymers soln, but this method reaction and separation temperature high (90-150 ℃), must be through centrifugation after reaction is finished, and centrifugal force when centrifugal * centrifugation time/polymer solution viscosity must be more than or equal to 50G-minutes/cp, better greater than 100G-minutes/cp, just can make residual metal effective elimination in the polymers soln, the method of employing standing separation can not make that residual metals content removes effectively in the polymers soln after reaction is finished, this just so that this method not only process is complicated, power consumption is high, and implements certain difficulty at full scale plant.
CN101333264A discloses a kind of method that a small amount of water removes polymer hydrogenating catalyst that adds, although amount of water is than U.S. US 5,281,696 amount of water decreases, reaction and separation temperature also have to a certain degree reduction, but still need the method separating catalyst solid residue with centrifugation after the reaction, so also make become more complicated and consume energy higher of removing of hydrogenation catalyst.
US5,104,972 disclose that a kind of silicate as sorbent material contacts with the polymers soln that contains VIII family metal hydrogenation catalyzer and the method for removing hydrogenation catalyst, this silicate comprises Calucium Silicate powder, Magnesium Silicate q-agent or diatomite, and the content of VIII family metal is less than 5ppm in the polymers soln that obtains.When the silicate sorbent material stirs when then separating with polymers soln, this contact process needs secondary or more than the secondary usually.Though this method can be removed the metal catalyst in the polymers soln to a certain extent, but sorbent material large usage quantity and to leave standstill time of processing longer when adopting standing separation, for example, in the sample 1 in the table 1 of the present invention, when room temperature, silicate consumption when being 10% based on the weight of polymers soln (concentration is the hydrogenation S-B-S triblock polymer solution of 16 % by weight), the nickel content that needs to mix in the solution that then left standstill after separation overnight just can make processing in 3 days drops to 0.3ppm (be equivalent to nickel content drops to 1.875ppm from 537ppm the straight polymer) from 86ppm; Perhaps as in the sample 8 in the table 1, need to just can be to the remainder catalyst effective elimination in the polymkeric substance with the further dilute polymer solution of solvent, for example, when the sorbent material consumption is polymers soln weight 2%, need to be with one times of solvent cut of polymers soln (concentration is the hydrogenation S-B-S triblock polymer solution of 16 % by weight), then mix 2hr and leave standstill separation overnight, just can make the nickel content in the solution after the processing drop to 0.4ppm (be equivalent to nickel content drops to 5ppm from 637ppm the straight polymer) from 51ppm; Though and the employing centrifugation can make remaining nickel effective elimination in the polymers soln, use complicated, the higher whizzer that consumes energy of manufacturing, can make the denitrating catalyst technological process become comparatively complicated, thereby increase the cost of product.
Summary of the invention
The object of the invention is to overcome in the prior art from polymers soln remove hydrogenation catalyst the time program complexity and the higher shortcoming of cost, a kind of simple, economic method of removing the hydrogenation catalyst in the unsaturated polymer hydrogenation post polymerization thing solution is provided.
The invention provides a kind of method of removing the hydrogenation catalyst in the polymers soln, contain polymkeric substance and hydrogenation catalyst in the described polymers soln, described hydrogenation catalyst contains trialkylaluminium cocatalyst and group VIII metallic compound and/or title complex Primary Catalysts, and the method may further comprise the steps:
(1) water is contacted with polymers soln in confined conditions with Powdered and/or granular silicate, form precipitation;
(2) solid-liquid separation is separated the gained mixture after step (1) contact and is removed precipitation,
Wherein, based on the weight of polymers soln, the addition of described water is the 0.01-2 % by weight, and the addition of described silicate is the 0.05-2 % by weight.
Method of removing the hydrogenation catalyst in the polymers soln provided by the invention, because employing silicate sorbent material and a small amount of water are removed the hydrogenation catalyst in the polymers soln, silicate and water make us occurring uncannily synergistic effect, and the effect of removing the hydrogenation catalyst in the polymers soln is significantly more a lot of than independent use silicate, water.For example, Ni content is 4.5ppm in the polymkeric substance after embodiment 1 processes, and in the identical situation of other conditions, only adds water and removes that Ni content is 75ppm in the polymkeric substance after the Comparative Examples 1 of the hydrogenation catalyst in the polymers soln is processed; Only add silicate and remove that Ni content is 65ppm in the polymkeric substance after the Comparative Examples 2 of the hydrogenation catalyst in the polymers soln is processed.In a kind of preferred implementation of the present invention, only by simple standing separation method, be about to after the gained mixture will leave standstill after the contact, inclining supernatant liquid remainder catalyst is removed effectively.Trace it to its cause may for water can with hydrogenation catalyst in promotor aluminum alkyls reaction generate gel particle, this reaction process is easy to implement, and speed of response is very fast, the particle of formation can adsorb Primary Catalysts and be condensed into very soon larger particle.After adding silicate, on the one hand, silicate can adsorb hydrogenation catalyst, on the other hand can planar water and the gel particle that forms of the promotor of hydrogenation catalyst, form the larger deposit seeds of particle diameter, thereby make absorption have that the precipitation of hydrogenation catalyst is easier to be separated from polymers soln.Method of the present invention is except reducing significantly the content of processing the catalyzer in the post polymerization thing solution, remove after the unsaturated polymer hydrogenation hydrogenation catalyst in the polymers soln owing to adopt comparatively cheap silicate sorbent material and a small amount of water, the reaction process of removing the hydrogenation catalyst in the polymers soln can not pollute polymers soln, and the process of removing the catalyst precipitation that the reaction of the hydrogenation catalyst in the polymers soln and separating reaction form is all fairly simple and consume energy low.In a kind of preferred implementation of the present invention, only just can make the remainder catalyst effective elimination by simple standing separation, make the method have very strong practicality.
Embodiment
According to a kind of method of removing the hydrogenation catalyst in the polymers soln of the present invention, contain polymkeric substance and hydrogenation catalyst in the described polymers soln, described hydrogenation catalyst contains trialkylaluminium cocatalyst and group VIII metallic compound and/or title complex Primary Catalysts, and the method may further comprise the steps:
(1) water is contacted with polymers soln in confined conditions with Powdered and/or granular silicate, form precipitation;
(2) solid-liquid separation is separated the gained mixture after step (1) contact and is removed precipitation,
Wherein, based on the weight of polymers soln, the addition of described water is the 0.01-2 % by weight, and the addition of described silicate is the 0.05-2 % by weight.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, can realize purpose of the present invention according to aforesaid method of the present invention, under the preferable case, wherein, based on the weight of polymers soln, the addition of described water is the 0.1-1.5 % by weight; Described addition Powdered and/or granular silicate is the 0.2-1.5 % by weight.In the inventive method the kind of used water not had particular requirement, can be deionized water, also can be the ordinary tap water.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, can realize purpose of the present invention according to aforesaid method of the present invention, to described water: the weight ratio of silicate is without particular requirement, can in wider scope, select, under the preferable case, described water: weight ratio Powdered and/or granular silicate is 1: 200 to 40: 1, is preferably 1: 100 to 20: 1, more preferably 1: 15 to 7.5: 1.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, the present invention to the kind of described Powdered and/or granular silicate without particular requirement, can be the various Powdered and/or granular silicate that can be used in the gel particles of absorption hydrogenation catalyst and planar water and hydrogenation catalyst formation, both natural Powdered and/or granular silicate can be, also synthetic Powdered and/or granular silicate can be.Powdered and/or granular silicate can be for water miscible, but can not be dissolved in the solvent in the polymers soln.Because the solvent in the polymers soln is generally in inert organic solvents such as Skellysolve A, octane, hexanaphthene, normal hexane, ether, toluene, the benzene one or more, therefore described silicate is preferably one or more in Calucium Silicate powder, Magnesium Silicate q-agent, diatomite, the solid silicone, more preferably diatomite.Described median size Powdered and/or granular silicate is preferably less than 0.5mm.Although greater than the Powdered and/or granular silicate granules of 0.5mm particle diameter because the restriction of active adsorption area, need more sorbent material during use, but the Powdered and/or granular silicate granules greater than the 0.5mm particle diameter makes things convenient for deposit seeds to separate from polymers soln, and therefore Powdered the and/or granular silicate granules greater than the 0.5mm particle diameter also can use.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, the present invention does not have particular requirement with Powdered and/or granular silicate with the condition that contacts of polymers soln to water described in the step (1), under the preferable case, the condition of contact can comprise: Contact Temperature is 0-150 ℃, preferred 10-80 ℃; Be 0.5-240 minute duration of contact, preferred 2-60 minute.Owing to the solution evaporation in the polymers soln, the vapour pressure of airtight reactor is 0.01-0.5MPa, is preferably 0.02-0.2MPa in the contact process.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, the present invention contacts the equipment that adopts to water and silicate sorbent material and polymers soln behind the hydrogenation and has no particular limits, as long as the mixing that can carry out therein polymers soln and remove the material of the hydrogenation catalyst in the polymers soln, this mixing equipment can be that stirred autoclave also can be the on-line mixing device, and this mixing process both can be intermittently, also can be continuous or semi-continuous.
Remove after the unsaturated polymer hydrogenation method of hydrogenation catalyst in the polymers soln according to of the present invention, the present invention does not have particular requirement to separating the method for removing precipitation described in the step (2), can adopt standing separation method, centrifugal separation, filtering separation method, under the preferable case, adopt the standing separation method.Described standing separation method is that inclining supernatant liquid after the gained mixture left standstill after will contacting.Adopt the standing separation method, do not need to set up extra separating device, thereby simplify the operation that after the unsaturated polymer hydrogenation, removes hydrogenation catalyst the polymers soln, improve catalyst removal efficient, reduce the Removal of catalyst cost.It should be explicitly made clear at this point, although the present invention also can adopt centrifugal separation to remove precipitation, but because the present invention has used water and silicate simultaneously, therefore centrifugation is not the necessary means that the present invention removes precipitation, just than standing separation, centrifugation can be removed precipitation more quickly, and if only have by centrifugation when Dan Jiashui removes hydrogenation catalyst in the polymers soln in the prior art and can realize effectively removing precipitation; And when singly adding silicate in the prior art and removing hydrogenation catalyst in the polymers soln, do not remove precipitation if do not adopt centrifugation, then need mixing time was extended to 3 days and need to leave standstill separation overnight or the polymers soln (16% SBS) after the consumption of silicate is based on dilution when being 2 % by weight, mix then hold over night separation more than 2 hours after need to diluting one times to polymers soln, and among the present invention during with the silicate of 0.5% water and 0.5%, polymers soln (10% butadiene-styrene block copolymer) contacts 20 minutes with water with silicate, leaving standstill 60 minutes metal contents in the polymers soln after the aftertreatment just can be below 10ppm.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, the present invention does not have particular requirement to the condition of standing separation method described in the step (2), and under the preferable case, the time of standing separation is 10-300 minute, preferred 30-180 minute; The temperature of standing separation is 0-100 ℃, preferred 20-70 ℃.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, the method also is included in step (1) before or the following steps of carrying out simultaneously:
(4) polymers soln is contacted with oxygenant.
Oxygenant can water and silicate with add before polymers soln mixes, also can when mixing with polymers soln, water and silicate add simultaneously, the adding of oxygenant has improved the valence state of hydrogenation catalyst, can improve to a certain extent sorbent material to the adsorption effect of catalyst precipitation particle.Oxygenant can for the mixture of hydrogen peroxide, molecular oxygen, oxygen and nitrogen and airborne one or more.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, described Primary Catalysts can be metallic compound and/or the title complex of periodic table of elements group VIII metal, be preferably one or more metallic compound and/or the title complex in iron, cobalt, nickel and the palladium, for activity and cost consideration, the more preferably compound of nickel and cobalt or title complex further are preferably compound and/or the title complex of nickel.The metallic compound of periodic table of elements group VIII metal is preferably the organic acid metal-salt, and organic acid wherein is preferably the paraffinic acid that contains 1-12 carbon atom and/or contains the salt of the naphthenic acid of 4-12 carbon atom.Described paraffinic acid more preferably contains the paraffinic acid of 4-8 carbon atom, further be preferably in formic acid, acetic acid, n Propanoic acid, isopropyl acid, butanic acid, isopropylformic acid, secondary butyric acid, uncle's butyric acid, positive valeric acid, isovaleric acid, secondary valeric acid, trimethylacetic acid, PIVALIC ACID CRUDE (25), n-caproic acid, secondary caproic acid, positive enanthic acid, secondary enanthic acid, n-caprylic acid, the secondary sad or 2 ethyl hexanoic acid one or more, further be preferably again nickel octoate, 2 ethyl hexanoic acid.Described naphthenic acid more preferably contains the naphthenic acid of 5-8 carbon atom, further is preferably cyclopropane-carboxylic acid, cyclopropaneacetic acid, cyclobutane formate, tetramethylene acetic acid, the tetramethylene propionic acid, cyclopentane-carboxylic acid, pentamethylene acetic acid, the pentamethylene propionic acid, ring penta ring butyric acid, 2-methylcyclopentane formic acid, 3-methylcyclopentane formic acid, 3-methylcyclopentane acetic acid, 3-methylcyclopentane propionic acid, naphthenic acid, Cyclohexaneacetic acid, the hexanaphthene propionic acid, 4-methylcyclohexane formic acid, suberane formic acid, suberane acetic acid, the suberane propionic acid, cyclooctane formic acid, cyclooctane acetic acid, in the cyclooctane propionic acid one or more.The specific examples of metal organic acid salt can be formate, acetate, propionic salt, 2-ethylhexoate, octylate, stearate, pentamethylene butyrates, the 3-methylcyclopentane formate of iron, cobalt, nickel and/or palladium, it perhaps is naphthenate, be preferably nickel salt, further preferably be preferably in nickel naphthenate, nickel octoate, the 2 ethyl hexanoic acid nickel one or more.The metallic compound of periodic table of elements group VIII metal can also be the alkane alkoxide of group VIII metal.Described alkanol is preferably the alcohol that contains 1-8 carbon atom, more preferably one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, sec.-amyl alcohol, tertiary amyl alcohol, neopentyl alcohol, n-hexyl alcohol, secondary hexyl alcohol, n-Heptyl alcohol, secondary enanthol or the 2-Ethylhexyl Alcohol.The specific examples of the alkane alkoxide of group VIII metal can be in 2-Ethylhexyl Alcohol nickel, 2-Ethylhexyl Alcohol cobalt, the 2-Ethylhexyl Alcohol iron nickel one or more.Part in the title complex of periodic table of elements group VIII metal comprises methyl ethyl diketone root, carbonyl etc.The specific examples of the title complex of periodic table of elements group VIII metal can be in ferric acetyl acetonade, acetylacetone cobalt, acetylacetonate nickel, eight carbonyl diurethane iron, cobalt octacarbonyl, the eight carbonyl diurethane nickel one or more.Primary Catalysts of the present invention can single kind use, and also can also two or more mix use.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, hydrogenation catalyst used therein of the present invention comprises and has formula Al (R)
3Trialkylaluminium as promotor, wherein, each R is identical or different, and each R is independently selected from has 1-6 carbon atom alkyl, the alkyl of preferred 1-4 carbon atom, particularly preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, neo-pentyl, n-hexyl and Sec-Hexyl, especially ethyl, sec.-propyl and isobutyl-; And the cycloalkyl with 3-6 carbon atom, preferred cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.The used trialkylaluminium of the present invention is such as being trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, amyl group dicyclohexyl aluminium, cyclopentyl dimethyl aluminium etc.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, generally, above-mentioned promotor and Primary Catalysts are mixed and prepare hydrogenation catalyst.
The unsaturated polymer for the treatment of hydrogenation in the inventive method can be homopolymer and/or the multipolymer of conjugated diene, when the unsaturated polymer for the treatment of hydrogenation was the multipolymer of conjugated diene, the multipolymer of conjugated diene can be the random and/or segmented copolymer of conjugated diene and vinyl-arene.In a preferred embodiment of the invention, the unsaturated polymer that uses in the inventive method be have 4-12 carbon atom conjugated diene homopolymer and/multipolymer, have the conjugated diene of 4-12 carbon atom and have the random and/or segmented copolymer of the vinyl-arene of 8-18 carbon atom.Aforementioned conjugated diene is preferably one or more in divinyl, pentadiene and the isoprene.The term " vinyl-arene " that uses in this article refers to by any aromatic hydrocarbons of vinyl substituted, for example benzene of vinyl substituted and/or naphthalene.In a preferred embodiment, vinyl-arene is substituted vinylbenzene and have alkyl in vinyl α position, especially have in the vinylbenzene of alkyl of 1-6 carbon atom one or more, more preferably alpha-methyl styrene and/or a α-ethyl styrene on vinylbenzene, the ring.In particularly preferred embodiment of the present invention, vinyl-arene is selected from one or more in vinylbenzene, alpha-methyl styrene and the α-ethyl styrene.In the present invention further optimization embodiment, unsaturated polymer is one or more in polyhutadiene, polyisoprene, styrene butadiene random copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-isoprene random copolymers, polystyrene-poly divinyl-polystyrene block copolymer, poly-(alpha-methyl styrene)-polyhutadiene-poly-(alpha-methyl styrene) segmented copolymer.
Should be appreciated that for the purpose of the present invention, the molecular weight of unsaturated polymer is not crucial for removing remaining hydrogenation catalyst.The molecular weight of the unsaturated polymer that the present invention uses can change in the scope of non-constant width, is 5000-1000000 such as its molecular weight, preferred 10000-300000, further preferred 25000-200000.
The unsaturated polymer itself that the inventive method is used is known, perhaps can be by the currently known methods preparation of those skilled in the art according to this area.For example, unsaturated polymer can prepare by radical polymerization, anionoid polymerization or cationoid polymerisation, and the method for preparing these polymkeric substance can be referring to US3, and 792,005 and US 3,431,323, the whole disclosure of these two is hereby incorporated by reference.
Prepare the solvent that unsaturated polymer of the present invention uses and be inert solvent, for example can be in Skellysolve A, octane, hexanaphthene, normal hexane, ether, toluene, the benzene one or more, be preferably the mixture of hexanaphthene and ether, the mixture of hexanaphthene and normal hexane.The related polymer solution concentration of the inventive method can change in wide region, and usually, based on the weight of polymers soln, the content of polymkeric substance is the 1-40 % by weight, preferred 2-20 % by weight.
The hydrogenation of unsaturated polymer of the present invention be make unsaturated polymer in solution with hydrogenation catalyst and hydrogen contact reacts.The solvent that this solution comprises is inert solvent, comprises Skellysolve A, octane, hexanaphthene, normal hexane, ether, toluene, benzene etc. or its mixture, for example is the mixture of hexanaphthene and ether, the mixture of hexanaphthene and normal hexane.Preferably, it is same that the solvent that uses of hydrogenation and polymerization prepare the solvent phase that unsaturated polymer uses.Described unsaturated polymer can partial hydrogenation or whole hydrogenation.Hydrogenation can carry out under the known common processing condition of prior art, for example can be referring to US3, and 595,942 and US 3,973,759, the whole disclosure of these two is hereby incorporated by reference.It should be noted that the selection for hydrogenation temperature and hydrogenation pressure, must guarantee that reaction mixture remains essentially in the liquid phase.
According to method of removing hydrogenation catalyst in the polymers soln of the present invention, the present invention is suitable for processing the polymeric system that contains different amount hydrogenation catalysts.Under the preferable case, the content of group VIII metallic compound or title complex Primary Catalysts is the 0.005-0.30g/100g polymkeric substance, more preferably the 0.01-0.10g/100g polymkeric substance; In the trialkylaluminium cocatalyst of aluminium with take the mol ratio of the Primary Catalysts of the group VIII metallic compound of metal and/or title complex as 1-10,3-8 more preferably.Process polymers soln afterwards through the inventive method, the catalyst content in the resulting polymers reduces greatly, and in the transition metal of its catalyzer, its weight content can less than 10ppm, reach acceptable degree.
Below by embodiment the present invention is carried out more detailed narration.But these embodiment must not think limitation of the scope of the invention.
Embodiment 1
In the 500L polymeric kettle, take n-Butyl Lithium as initiator, the mixture of hexanaphthene and normal hexane (weight percent of hexanaphthene is 87%) is the synthetic butadiene-styrene block polymer of solvent.In the gained polymerisate, butadiene-styrene block copolymer concentration is 10.0 % by weight based on whole polymerization system, and the molecular weight of this segmented copolymer is 6.5 ten thousand, and vinylbenzene is 3 to 7 with the weight ratio of butadiene monomer unit.
With triisobutyl aluminium (synthetic rubber plant, the Yanshan Mountain, Beijing, technical grade, concentration 3g/L) and nickel naphthenate (synthetic rubber plant, the Yanshan Mountain, Beijing, technical grade, concentration 4g/L) and) be to mix at 4: 1 according to mol ratio (by metal), in 50 ℃ of lower ageings 30 minutes, then it is added in the butadiene-styrene block copolymer solution obtained above, and stirs.Then the butadiene-styrene block copolymer solution that 1200mL is contained hydrogenation catalyst adds in the autoclave after 2.0L purifies with high-purity hydrogen and carries out hydrogenation reaction.The hydrogenation reaction temperature is controlled at about 65 ℃, reaction pressure is 3.0MPa (gauge pressure), mixing speed is 600rpm, and catalyst levels is 0.07g Ni/100g butadiene-styrene block copolymer reaction 2 hours, and divinyl section degree of hydrogenation is greater than 98% in the polymkeric substance.
Getting hydrogenation post polymerization thing solution 1200mL joins in the 2L closed reactor, by water bath with thermostatic control hydrogenation post polymerization thing solution is heated to 70 ℃, then add weight based on hydrogenation post polymerization thing solution in the polymers soln after the heating and be 0.5% deionized water and be that 0.5% particle diameter is the diatomite (Qingdao Chuanyi Diatomite Co., Ltd.'s production) of 0.3mm based on the weight of hydrogenation post polymerization thing solution, under 600rpm, mix 20 minutes.Mixed polymers soln adopts the standing separation method to remove hydrogenation catalyst, and the standing separation temperature is 60 ℃, and the time is 60 minutes.Leaving standstill rear container bottom has the part black precipitate, and the upper strata is water white polymers soln.Separate the polymers soln that obtains and dry to constant weight in 50 ℃ of loft drier with the ethanol cohesion is rear, then survey metal content in the polymkeric substance with plasma emission spectrometry, the results are shown in Table 1.
Embodiment 2
Basic condition is identical with embodiment 1, and just water and diatomite and polymers soln mixing time in reactor are respectively 2,10,30,60 minutes, the results are shown in Table 1.
Embodiment 3
Basic condition is identical with embodiment 1, and just water and diatomite and polymers soln mixing temperature in reactor are 60,40,25 ℃, the results are shown in Table 1.
Table 1. mixing temperature and time are on the impact of hydrogenation catalyst removal effect
Can be found out by table 1 result, when mixing temperature is normal temperature to 70 ℃, when mixing time is 2 to 60 minutes, fully mix by the water of interpolation 0.5% weight and the sorbent material of 0.5% weight in the polymeric system after hydrogenation, then standing separation all can effectively be removed the remainder catalyst in the hydrogenation post polymerization thing solution after 60 minutes.
Embodiment 4
Change respectively institute's amount of water 0.1%, 1.0%, 1.5% of hydrogenation post polymerization thing solution into based on the weight of hydrogenation post polymerization thing solution, mixing time is 30 minutes, and mixing temperature is 70 ℃, and all the other are identical with embodiment 1, the results are shown in Table 2.
Embodiment 5
With adding the diatomite amount change respectively 0.2%, 1.0%, 1.5% of hydrogenation post polymerization thing solution into based on the weight of hydrogenation post polymerization thing solution, mixing time is 30 minutes, mixing temperature is 70 ℃, all the other are identical with embodiment 1, the results are shown in Table 2.
Embodiment 6
Basic condition is identical with embodiment 1, and just adding sorbent material is Calucium Silicate powder (Jiangsu is inspired confidence in gloomy trade Co., Ltd and produced particle diameter 0.3mm), the results are shown in Table 2.
Embodiment 7
Basic condition is identical with embodiment 1, and just adding sorbent material is Magnesium Silicate q-agent (Yixing City foundation chemical industry company limited produces, median size 0.3mm), the results are shown in Table 2.
Embodiment 8
Basic condition is identical with embodiment 1, and just adding sorbent material is spherical silica gel (the plentiful molecular sieve in Dalian Manufacturing Co., Ltd, particle diameter 2.0mm), the results are shown in Table 2.
Comparative Examples 1
Basic condition is identical with embodiment 1, just removes the weight that only adds in the mixing process of hydrogenation catalyst based on hydrogenation post polymerization thing solution and is 1.0% deionized water and do not add diatomite adsorbant, the results are shown in Table 2.
Comparative Examples 2
Basic condition is identical with embodiment 1, just removes the weight that only adds in the mixing process of hydrogenation catalyst based on hydrogenation post polymerization thing solution and is 1.0% diatomite adsorbant and do not add deionized water, the results are shown in Table 2.
Add the different water yields in table 2. polymers soln to the removal effect of remainder catalyst
Can be found out by table 2 result, add the water of 0.1-1.5% and the various silicate of 0.2-1.5% in the hydrogenation polymers soln and all can effectively get hydrogenation catalyst except wherein.In the identical situation of other side conditionally complete, the sorbent material consumption increases better to the removal effect of remainder catalyst.And Dan Jiashui or silicate sorbent material can not the remaining hydrogenation catalysts of effective elimination.
Embodiment 9
Basic condition is identical with embodiment 1, and just the standing separation temperature is respectively 40 ℃, 25 ℃, the results are shown in Table 3.
Embodiment 10
Basic condition is identical with embodiment 1, and just the standing separation time is 30 minutes, 90 minutes, 120 minutes and 180 minutes, the results are shown in Table 3.
The different standing separation conditions of table 3. are on the impact of remainder catalyst removal effect
Can be found out by table 3 result, when the standing separation temperature is 25-60 ℃, all can makes the hydrogenation catalyst effective elimination in the polymers soln when standing separation time is 30-180 minute, along with the standing separation temperature raises and the standing separation time lengthening, separating effect improves.
Embodiment 11
Basic condition is identical with embodiment 1, adopt the method for centrifugation to remove hydrogenation catalyst after just water and diatomite adsorbant mix with polymers soln, the centrifugation temperature is 60 ℃, and the centrifugation time is respectively 3min, and the centrifugation rotating speed is respectively 3000rpm.Nickel content is 0.1ppm in the separation post polymerization thing, and aluminium content is 1.0ppm.
Embodiment 12
Basic condition is identical with embodiment 1, and just the hydrogenation catalyst consumption is the 0.05gNi/100g polymkeric substance, in the triisobutyl aluminium of aluminium with take the mol ratio of the nickel naphthenate of metal as 4: 1, nickeliferous 2.5ppm in the polymkeric substance that obtains contains aluminium 8.5ppm.
Embodiment 13
Basic condition is identical with embodiment 1, and just the hydrogenation catalyst consumption is the 0.03gNi/100g polymkeric substance, in the triisobutyl aluminium of aluminium with take the mol ratio of the nickel naphthenate of metal as 4: 1.Nickeliferous 2.0ppm in the polymkeric substance that obtains contains aluminium 7.5ppm.
Embodiment 14
Basic condition is identical with embodiment 1, and just polymer solution concentration is 16.0 % by weight, and after the method processing identical with embodiment 1, nickeliferous 6.9ppm in the polymkeric substance contains aluminium 17.0ppm.
Embodiment 15
Basic condition is identical with embodiment 1, and just polymer solution concentration is 16.0 % by weight, and the mixing temperature of water and silicate and polymers soln is 25 ℃, and after the method processing identical with embodiment 1, nickeliferous 7.8ppm in the polymkeric substance contains aluminium 18.5ppm.
Embodiment 16
Basic condition is identical with embodiment 1, and just polymericular weight is 10.0 ten thousand, and after the method processing identical with embodiment 1, nickeliferous 5.5ppm in the polymkeric substance contains aluminium 17.0ppm.
Embodiment 17
Basic condition is identical with embodiment 1, just water and diatomite contacts with polymers soln that adding 20mL concentration is 30 % by weight aqueous hydrogen peroxide solutions stirring 10 minutes in the forward direction polymers soln, then add entry and diatomite, obtain remaining nickel content 4.0ppm in the polymkeric substance, aluminium content 12.0ppm.
Embodiment 18
Basic condition is identical with embodiment 1, when just water and diatomite contact with polymers soln in the polymers soln adding 20mL concentration be 30 % by weight aqueous hydrogen peroxide solutions, obtain remaining nickel content 3.8ppm in the polymkeric substance, aluminium content 11.5ppm.
Embodiment 19
Basic condition is identical with embodiment 1, does not stop drum oxygen when just water and diatomite contact with polymers soln in polymers soln, and oxygen flow is 2.0mL/min, obtains remaining nickel content 3.0ppm in the polymkeric substance, aluminium content 9.5ppm.
Embodiment 20
Basic condition is identical with embodiment 1, does not stop the drum air when just water and diatomite contact with polymers soln in polymers soln, and air flow quantity is 3.0mL/min, obtains remaining nickel content 3.1ppm in the polymkeric substance, aluminium content 9.8ppm.
Claims (10)
1. method of removing the hydrogenation catalyst in the polymers soln, contain polymkeric substance and hydrogenation catalyst in the described polymers soln, described hydrogenation catalyst contains trialkylaluminium cocatalyst and group VIII metallic compound and/or title complex Primary Catalysts, and the method may further comprise the steps:
(1) water is contacted with polymers soln in confined conditions with Powdered and/or granular silicate, form precipitation;
(2) solid-liquid separation is separated the gained mixture after step (1) contact and is removed precipitation,
Wherein, based on the weight of polymers soln, the addition of described water is the 0.01-2 % by weight, and the addition of described silicate is the 0.05-2 % by weight.
2. method according to claim 1, wherein, based on the weight of polymers soln, the addition of described water is the 0.1-1.5 % by weight, the addition of described silicate is the 0.2-1.5 % by weight.
3. method according to claim 1 and 2, wherein, described water: weight ratio Powdered and/or granular silicate is 1: 100 to 20: 1, is preferably 1: 15 to 7.5: 1.
4. the described method of any one according to claim 1-3, wherein, described silicate is one or more in Calucium Silicate powder, Magnesium Silicate q-agent, diatomite, the solid silicone.
5. method according to claim 1, wherein, the Contact Temperature of water and Powdered and/or granular silicate and polymers soln is 0-150 ℃ in the step (1), preferably 10-80 ℃; Be 0.5-240 minute duration of contact, preferred 2-60 minute.
6. method according to claim 1, wherein, the method that precipitation is removed in the separation in the step (2) is the standing separation method.
7. method according to claim 6, wherein, the time of standing separation is 10-300 minute, preferred 30-180 minute; The temperature of standing separation is 0-100 ℃, preferred 20-70 ℃.
8. method according to claim 1, wherein, described group VIII metallic compound and/or title complex are nickel compound and/or nickel complex.
9. method according to claim 8, wherein, described nickel compound is the organic acid nickel salt, described organic acid is the naphthenic acid that has the paraffinic acid of 1-12 carbon atom or have 4-12 carbon atom, and described organic acid nickel salt is preferably one or more in nickel naphthenate, 2 ethyl hexanoic acid nickel, the nickel octoate; The promotor of described hydrogenation catalyst is for having formula Al (R)
3Trialkylaluminium, wherein, each R is identical or different, and each R is independently selected from the alkyl with 1-6 carbon atom or has the cycloalkyl of 3-6 carbon atom; Described promotor is preferably one or more in triisobutyl aluminium, triisopropylaluminiuand and the triethyl aluminum.
10. according to claim 1 or 9 described methods, wherein, the content of group VIII metallic compound and/or title complex Primary Catalysts is the 0.005-0.30g/100g polymkeric substance, is preferably the 0.01-0.10g/100g polymkeric substance; In the trialkylaluminium cocatalyst of aluminium with take the mol ratio of the group VIII metallic compound of metal and/or title complex Primary Catalysts as 1-10, be preferably 3-8.
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| CN106967190A (en) * | 2016-01-14 | 2017-07-21 | 中国石油化工股份有限公司 | Hydrogenated styrene-conjugated diene copolymer and its removal method of catalyst and preparation method |
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