CN106749782B - The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment - Google Patents
The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment Download PDFInfo
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Abstract
The invention discloses a kind of removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment.This method comprises the following steps that: the oxidation of polymer solution, the chelating of catalyst metals and liquid separation and precipitating drying.The present invention is solved when handling high viscosity polymer (viscosity is greater than 600mPas) glue, the problem that causes metal removal effect poor slowly and incomplete due to aoxidizing by the oxidation stage addition hydrochloric acid in polymer solution.This method be suitable for various viscositys polymer solution, oxidation rate is fast, and later during only need to carry out stand liquid separation subject polymer solution can be obtained, be not necessarily to centrifugation apparatus, not only saved equipment cost, and saved time cost.
Description
Technical field
The present invention relates to a kind of post-processing technology of polymer, especially a kind of unsaturated polymer residure after hydrogenation treatment catalysis
The removal methods of al and ni in agent.
Background technique
In polymer especially hydrogenated polymers often contain various metal impurities, these impurity by oxidation, it is photochemical with
And the series reactions such as metallization, performance of polymer, such as coloration, stability, electrical property etc. can be made to deteriorate rapidly, and also
It may interfere with the successive modified of polymer, therefore a set of product purification method must be set up to hydrogenated polymers, metallic residue
Removing.Nickel aluminum catalytic hydrogenation system is widely used in polymerizeing due to the advantages that highly selective, cheap, hydrogenation efficiency is high
In the hydrogenation reaction of object, there are many document reports for the removing of metallic residue in the system, be broadly divided into wet process and done
Method.So-called wet process refers to: the aqueous solution of certain reagent being added in hydrogenated polymers solution, is made in reagent and polymer solution
Metal ion reaction generate and can be dissolved in water and be insoluble in the sediment of polymer solution, the water of metal ion is then demultiplex out
Mutually achieve the purpose that remove metal；So-called dry method refers to: adding one kind into hydrogenated polymers solution and is free of or containing only a small amount of
Certain reagent of water, this reagent can be reacted with the metal ion in polymer solution generate it is a kind of insoluble in polymer solution
Then sediment is separated the sediment containing metallic residue by separation means.
United States Patent (USP) US3780138 discloses the metallic residue in citric acid method removing hydrogenated polymers solution, specifically such as
Under: first hydrogenated polymers solution is pre-processed with oxidant such as oxygen, hydrogen peroxide, acyl peroxide etc., is made at a low price
Metal is oxidized to high-valency metal；It is come into full contact with again with the aqueous citric acid solution containing lower alcohol and above-mentioned glue, keeps polymer molten
High-valency metal in liquid is dissolved in aqueous citric acid solution；Then isolated from the solution of standing the organic phase containing polymer and
Citric acid solution water phase containing dissolution metal, to realize the removing of metallic residue, Ni removal efficiency is 98%.The above method
The disadvantage is that being easy to produce emulsion, mutually separation is deteriorated, to influence the removing of metallic residue.
The characteristics of United States Patent (USP) US4992529 discloses a kind of mixed acid process, this method be by monocarboxylic acid with have
Metal reaction in machine phase, generates the carboxylate insoluble in organic phase, and the inorganic acid reaction in the carboxylate and mixed acid generates
The inorganic salts being soluble in the aqueous phase, carboxylic acid, which is reduced, to be come back in organic phase, then generates carboxylic with the metal reaction in polymer solution
Hydrochlorate so recycles, until the metal in polymer solution is completely transferred in water phase, to realize the removing of metallic residue.
Herein, carboxylic acid serves as phase transfer catalyst effect.This method thinking is relatively new, but removal effect is unsatisfactory, in addition
Also need a large amount of water.
United States Patent (USP) US4396761 is using the metal in the Alpha-hydroxy sulfonic acid aqueous solution and polymer solution of 0.1%-10%
The sulfonate being soluble in the aqueous phase is reacted into, the removing of metallic residue is then realized by mutually separation.The characteristics of this method is residual
Alpha-hydroxy sulfonic acid in a polymer solution can be removed by heating or vacuum technique.
Compared with above-mentioned wet process, biochemical treatment of the dry method due to not using or only with a small amount of water without waste water is asked
Topic, thus it is more advantageous.For example, by using the absorption method of the adsorbents such as active carbon, diatomite or atlapulgite.United States Patent (USP)
US5089541 uses a kind of brown coal base active carbon through pickling, and dosage is the 0.2%-10% of glue.Detailed process is as follows:
It is passed through nitrogen 1 hour that oxygen content is 3% at 60-90 DEG C, a certain amount of active carbon is then added, stirs 2-3 days, it is overnight heavy
Drop, as a result tenor reaches requirement.The shortcomings that this method is that the sedimentation time is too long, is had much room for improvement.United States Patent (USP) US5104972 is adopted
Use diatomite as adsorbent, dosage is the 0.7-10% of glue, and adsorbent hydroxyl aluminum is 30 minutes, it is sufficient to be removed from glue
Level of the Ni to requirement.Japanese Kuraray company (special open 2002-317008) is using atlapulgite to adding hydrogen diene polymer
Middle metal ion is removed, and dosage is 1-500 times of metal quality, is stirred 30 minutes, is filtered under diminished pressure transparent through sedimentation
Glue.Although the above method is simple and easy to do, when Polymer Solution Viscosity is larger, effect is become very poor, and is operated
Become to be not easy to carry out, especially to the biggish polymer solution filter operation of viscosity.
Another dry method is inorganic salts method.In European patent EP 372213, using water-soluble silicate, borate or
The aqueous solution of carbonate can load to inorganic salts on porous carrier if necessary, or be made using ethoxylated fatty acid ester
For dispersing agent, preferable metal removal effect can reach.
Many patent reports another dry method, i.e. dicarboxylic acids method.The step of this method, is as follows: adding first into glue
Enter a certain amount of oxidant, metal is oxidized to high-valence state, dicarboxylic acids is then added and reacts generation precipitating with metal ion, most
Pass through centrifuge separation removing metallic residue afterwards.One key factor of this method is the suitable dicarboxylic acids of selection, be may be selected
Dicarboxylic acids there are many kinds of, as malonic acid, succinic acid, fumaric acid, maleic acid, 2,3- dyhydrobutanedioic acid, oneself
Diacid, azelaic acid, decanedioic acid and phthalic acid etc..Another key factor of this method is dissolution of the dicarboxylic acids in glue
Property problem, select suitable solubilizer always and be the emphasis of research and development.United States Patent (USP) US4595749 uses lower aliphatic alcohols such as first
As solubilizer, the characteristics of this kind of alcohol, is dissolved in water for alcohol, ethyl alcohol and isopropanol, is mutually separated clearly, but since lower alcohol is to poly-
The recycling of bonding solvent creates great difficulties, while the sedimentation time is also too long, therefore there is no industrialized.United States Patent (USP)
US5073621 discloses another solubilizer, water.Dicarboxylic acids is first dissolved in water by this method, is then then added to glue
In, can preferably remove the metal in glue in this way, however this method is easy to that glue is caused to emulsify, be unfavorable for dicarboxylic acids with
The reaction of metal ion, influences the removal efficiency of metal, and technique is difficult to control.Chinese patent CN1067898 discloses a kind of polymerization
Dioxygen is added in hydrogenated butadiene-styrene random copolymerization composition glue liquid in the removal methods of object residure after hydrogenation treatment metallic catalyst
Decanedioic acid, as precipitating reagent, is dissolved in diethylene glycol monobutyl ether aqueous solution that decanedioic acid is made is molten as oxidant, decanedioic acid by water
Liquid substantially increases the removal effect of metal in glue, especially when glue viscosity is in 50-600mPas, remains to preferable
Remove metallic residue.The defect of this method is: (viscosity is greater than 600mPas), oxidation when handling high viscosity polymer glue
What is carried out is very slow, and not exclusively, leads to metal removal poor effect.
Summary of the invention
The purpose of the present invention is to provide a kind of removings of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment
Method, this method is to metal removal significant effect in various viscosity polymer especially high viscosity polymer, easy to operate, cost
Low, industrial prospect is wide.
Above-mentioned purpose of the invention is achieved in that the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment
Removal methods comprise the following steps that:
The oxidation of S1, polymer solution: aoxidizing polymer solution using hydrogen peroxide and hydrochloric acid, the addition of hydrogen peroxide
Amount is 1-20 times of the amount of the substance of metal in polymer solution, and the additional amount of hydrochloric acid is the substance of metal in polymer solution
0.1-5.0 times of amount, oxidizing reaction temperature are 30-100 DEG C, and oxidation time is 30-240 minutes；
The chelating of S2, catalyst metals: preparing the chelating liquid that mass concentration is 0.2-5%, and the solute of the chelating liquid is two
First carboxylic acid, solvent are diethylene glycol monobutyl ether aqueous solution, and the mass concentration of the solvent is 35-85%, and chelating liquid is added to step
Suddenly it is reacted in the polymer solution after S1 is aoxidized, chelates the additional amount of liquid in terms of dicarboxylic acids, be golden in polymer solution
1-5 times of the amount of the substance of category, chelatropic reaction temperature are 30-100 DEG C, and the chelatropic reaction time is 30-180 minutes；
S3, liquid separation and precipitating drying: the polymer solution after S2 is chelated is transferred to separatory funnel, stands 60 minutes,
Solution is divided into three layers, divides and goes lower two layers, upper solution is the solution for being stripped of catalyst metals；Then by upper solution according to
Volume ratio 1:1 is injected into dehydrated alcohol, after flocculation sedimentation goes out polymer, extremely by drying in precipitating 50 DEG C of vacuum ovens of merging
Constant weight obtains final polymer.
The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step S1
In, the oxidizing reaction temperature is preferably 50-70 DEG C, and the oxidation time is preferably 60-120 minutes.
The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step S2
In, the dicarboxylic acids is preferably decanedioic acid or adipic acid.
The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step S2
In, the mass concentration of the diethylene glycol monobutyl ether aqueous solution is preferably 50-70%.
The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step S2
In, the additional amount of the chelating liquid is preferably 1.5-2.5 times of metal in polymer solution in terms of dicarboxylic acids.
The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step S2
In, the chelatropic reaction temperature is preferably 50-70 DEG C, and the chelatropic reaction time is preferably 60-120 minutes.
The removal methods of al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, wherein institute
Stating unsaturated polymer is preferably the homopolymer of conjugated diene, the copolymer of conjugated diene or conjugated diene and benzene second
The copolymer of alkene.
The invention has the benefit that hydrochloric acid is added by the oxidation stage in polymer solution, so that various viscositys
The fast simultaneous oxidation of the oxidation rate of polymer glue is complete, and metal removal effect is good, solves the prior art in processing high viscosity
When polymer (viscosity is greater than 600mPas) glue, the problem of metal removal effect difference slowly and incomplete due to aoxidizing.This
Method is suitable for the polymer solution of various viscositys, and oxidation rate is fast, and later during only need to carry out standing liquid separation
Subject polymer solution can be obtained, be not necessarily to centrifugation apparatus, not only saved equipment cost, and saved time cost.
Specific embodiment
The present invention is further illustrated by the following examples, and however, the present invention is not limited to these examples.
One, the formula for chelating liquid is as shown in table 1:
The formula of the chelating liquid of table 1.
Two, tenor is tested using ICP in polymer solution, method standard GB/T17476-1998.
Embodiment 1
Take plus hydrogen after polymer (add hydrogen before for isoprene/butadiene-styrene block copolymer) solution 100g set
In the 500mL three-necked flask for being equipped with condenser pipe, detection Polymer Solution Viscosity is 450mPas, and Ni content is 329ppm, Al
Content is 456ppm.The H of 30% concentration is sequentially added into reaction flask2O2The hydrochloric acid 0.67mL of aqueous solution 2.3mL, 37% concentration,
It is reacted 120 minutes under the conditions of 65 DEG C of temperature.
Then 91.0g chelating agent P3 is added into reaction flask, is reacted 120 minutes under the conditions of 65 DEG C of temperature.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 2
Take plus hydrogen after polymer (add hydrogen before for star isoprene/butadiene-styrene block copolymer) solution is about
For 100g in the 500mL three-necked flask for being equipped with condenser pipe, detection Polymer Solution Viscosity is 1030mPas, and Ni content is
346ppm, Al content 567ppm.The H of 30% concentration is sequentially added into reaction flask2O2The salt of aqueous solution 5.5mL, 37% concentration
Sour 1.33mL reacts 240 minutes at 30 DEG C.
Then to 272.0g chelating agent P1 is added in reaction flask, reacted 180 minutes at 30 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 3
Take plus hydrogen after polymer (add hydrogen before for polyisoprene) solution about 100g in being equipped with tri- mouthfuls of 500mL of condenser pipe
In flask, detection Polymer Solution Viscosity is 50mPas, and Ni content is 352ppm, Al content 621ppm.Into reaction flask
Sequentially add the H of 30% concentration2O2The hydrochloric acid 0.03mL of aqueous solution 1.48mL, 37% concentration react 100 minutes at 70 DEG C.
Then to 59.0g chelating agent P6 is added in reaction flask, reacted 120 minutes at 70 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 4
Take plus hydrogen after polymer (add hydrogen before for butadiene-isoprene copolymer) solution about 100g in being equipped with condenser pipe
500mL three-necked flask in, detection Polymer Solution Viscosity is 860mPas, and Ni content is 587ppm, and Al content is
891ppm.The H of 30% concentration is sequentially added into reaction flask2O2The hydrochloric acid 0.21mL of aqueous solution 0.44mL, 37% concentration, 100 DEG C
Lower reaction 30 minutes.
Then to 174.0g chelating agent P2 is added in reaction flask, reacted 30 minutes at 100 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 5
Take plus hydrogen after polymer (add hydrogen before for butadienestyrene copolymer) solution about 100g in being equipped with condenser pipe
In 500mL three-necked flask, detection Polymer Solution Viscosity is 340mPas, and Ni content is 470ppm, Al content 837ppm.
The H of 30% concentration is sequentially added into reaction flask2O2The hydrochloric acid 0.38mL of aqueous solution 0.8mL, 37% concentration react 180 at 50 DEG C
Minute.
Then to 79.0g chelating agent P4 is added in reaction flask, reacted 150 minutes at 50 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 6
Take plus hydrogen after polymer (add hydrogen before for star isoprene styrene di-block copolymer) solution about 100g in
It is equipped in the 500mL three-necked flask of condenser pipe, detection Polymer Solution Viscosity is 550mPas, and Ni content is 350ppm, and Al contains
Amount is 840ppm.The H of 30% concentration is sequentially added into reaction flask2O2The hydrochloric acid 0.73mL of aqueous solution 5.67mL, 37% concentration,
It is reacted 120 minutes at 60 DEG C.
Then to 150.0g chelating agent P5 is added in reaction flask, reacted 120 minutes at 60 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 7
Take plus hydrogen after polymer (add hydrogen before for isoprene-butadiene/styrene di-block copolymer) solution is about
For 100g in the 500mL three-necked flask for being equipped with condenser pipe, detection Polymer Solution Viscosity is 580mPas, and Ni content is
410ppm, Al content 945ppm.The H of 30% concentration is sequentially added into reaction flask2O2Aqueous solution 4.29mL, 37% concentration
Hydrochloric acid 1.24mL reacts 80 minutes at 80 DEG C.
Then to 170.0g chelating agent P8 is added in reaction flask, reacted 80 minutes at 80 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 8
Take plus hydrogen after polymer (add hydrogen before for star polybutadiene) solution about 100g in the 500mL tri- for being equipped with condenser pipe
In mouth flask, detection Polymer Solution Viscosity is 640mPas, and Ni content is 358ppm, Al content 923ppm.To reaction flask
In sequentially add the H of 30% concentration2O2The hydrochloric acid 1.60mL of aqueous solution 4.11mL, 37% concentration react 60 minutes at 90 DEG C.
Then to 163.0g chelating agent P8 is added in reaction flask, reacted 60 minutes at 90 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 9
Take plus hydrogen after polymer (add hydrogen before for star polyisoprene) solution about 100g in the 500mL for being equipped with condenser pipe
In three-necked flask, detection Polymer Solution Viscosity is 680mPas, and Ni content is 423ppm, Al content 910ppm.To reaction
The H of 30% concentration is sequentially added in bottle2O2The hydrochloric acid 0.2mL of aqueous solution 2.1mL, 37% concentration react 100 minutes at 70 DEG C.
Then to 83.0g chelating agent P9 is added in reaction flask, reacted 120 minutes at 70 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 10
Take plus hydrogen after polymer (add hydrogen before for isoprene/butadiene-styrene di-block copolymer) solution is about
For 100g in the 500mL three-necked flask for being equipped with condenser pipe, detection Polymer Solution Viscosity is 420mPas, and Ni content is
323ppm, Al content 743ppm.The H of 30% concentration is sequentially added into reaction flask2O2Aqueous solution 3.37mL, 37% concentration
Hydrochloric acid 0.98mL reacts 100 minutes at 70 DEG C.
Then to 67.0g chelating agent P9 is added in reaction flask, reacted 120 minutes at 70 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 11
Take plus hydrogen after polymer (add hydrogen before for star isoprene/butadiene-styrene di-block copolymer) solution
For about 100g in the 500mL three-necked flask for being equipped with condenser pipe, detection Polymer Solution Viscosity is 880mPas, and Ni content is
335ppm, Al content 691ppm.The H of 30% concentration is sequentially added into reaction flask2O2Aqueous solution 3.83mL, 37% concentration
Hydrochloric acid 0.93mL reacts 120 minutes at 65 DEG C.
Then to 126.0g chelating agent P2 is added in reaction flask, reacted 120 minutes at 65 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.The removal effect of catalyst is shown in Table 2.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 12
Take plus hydrogen after polymer (add hydrogen before for butadiene-isoprene styrene random copolymer) solution about 100g in
It is equipped in the 500mL three-necked flask of condenser pipe, detection Polymer Solution Viscosity is 210mPas, and Ni content is 352ppm, and Al contains
Amount is 640ppm.The H of 30% concentration is sequentially added into reaction flask2O2The hydrochloric acid 0.88mL of aqueous solution 2.43mL, 37% concentration,
It is reacted 120 minutes at 65 DEG C.
Then to 48.0g chelating agent P11 is added in reaction flask, reacted 120 minutes at 65 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.The removal effect of catalyst is shown in Table 2.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 13
Take plus hydrogen after polymer (add hydrogen before for butadiene-isoprene copolymer) solution about 100g in being equipped with condenser pipe
500mL three-necked flask in, detection Polymer Solution Viscosity is 320mPas, and Ni content is 411ppm, and Al content is
651ppm.The H of 30% concentration is sequentially added into reaction flask2O2The hydrochloric acid 0.92mL of aqueous solution 3.18mL, 37% concentration, 65 DEG C
Lower reaction 120 minutes.
Then to 126.0g chelating agent P3 is added in reaction flask, reacted 120 minutes at 65 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 14
Take plus hydrogen after polymer (add hydrogen before for star butadiene/isoprene-styrene block copolymer) solution is about
For 100g in the 500mL three-necked flask for being equipped with condenser pipe, detection Polymer Solution Viscosity is 830mPas, and Ni content is
235ppm, Al content 410ppm.The H of 30% concentration is sequentially added into reaction flask2O2Aqueous solution 1.96mL, 37% concentration
Hydrochloric acid 0.57mL reacts 100 minutes at 70 DEG C.
Then to 388.0g chelating agent P7 is added in reaction flask, reacted 120 minutes at 70 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 15
Take plus hydrogen after polymer (add hydrogen before for butadiene styrene random copolymer) solution about 100g condense in being equipped with
In the 500mL three-necked flask of pipe, detection Polymer Solution Viscosity is 550mPas, and Ni content is 470ppm, and Al content is
866ppm.The H of 30% concentration is sequentially added into reaction flask2O2The hydrochloric acid 1.2mL of aqueous solution 4.1mL, 37% concentration, at 70 DEG C
Reaction 100 minutes.
Then to 82.0g chelating agent P4 is added in reaction flask, reacted 120 minutes at 70 DEG C.
Solution is transferred in separatory funnel afterwards after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is
Egg white shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
Embodiment 16
Take plus hydrogen after polymer (add hydrogen before for star polyisoprene) solution about 100g in the 500mL for being equipped with condenser pipe
In three-necked flask, detection Polymer Solution Viscosity is 540mPas, and Ni content is 452ppm, Al content 953ppm.To reaction
The H of 30% concentration is sequentially added in bottle2O2The hydrochloric acid 1.27mL of aqueous solution 4.39mL, 37% concentration react 100 minutes at 70 DEG C.
Then to 87.0g chelating agent P10 is added in reaction flask, reacted 120 minutes at 70 DEG C.
Solution is transferred in separatory funnel after reaction, stands 60 minutes under room temperature, solution is divided into three layers, and upper layer is egg
Clear shape opaque liquid, middle layer are semi-transparent clear solution, and lower layer is light green clear solution.
Taking upper solution, 1:1 is injected into dehydrated alcohol by volume, and the polymer to flocculate out is transferred to 50 DEG C of vacuum drying
It dries to constant weight in case to get product.
Using ICP test method, the polymer of polymer and Removal of catalyst metal to non-Removal of catalyst metal into
Row detection, show that comparing result is shown in Table 2.
2 catalyst metals removal effect of table
From Table 2, it can be seen that viscosity range from the polymer glue of 50-1030mPas by means of the present invention from
The content of al and ni is very low in polymer after reason, and total content is not higher than 15ppm, is all satisfied in products application requirement.In addition,
The present invention can make processing glue viscosity range be expanded to 1000mPas, greatly increase by adjusting the concentration of dicarboxylic acids
The applicability of the method.
Hydrochloric acid is added by the oxidation stage in polymer solution in the present invention, so that the oxygen of the polymer glue of various viscositys
Change the fast simultaneous oxidation of speed it is complete, metal removal effect is good, solve processing high viscosity polymer (viscosity be greater than 600mPa
S) slowly and incomplete due to aoxidizing when glue, the problem of metal removal effect difference.
This method is suitable for the polymer solution of various viscositys, and oxidation rate is fast, and later during only need to be into
Row, which stands liquid separation, can be obtained subject polymer solution, centrifugation apparatus is not necessarily to, when not only having saved equipment cost, and having saved
Between cost.Method and process of the invention is stablized, and simple and easy to do, industrial prospect is wide.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (7)
1. the removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment, which is characterized in that including following work
Skill step:
The oxidation of S1, polymer solution: aoxidizing polymer solution using hydrogen peroxide and hydrochloric acid, and the additional amount of hydrogen peroxide is
1-20 times of the amount of the substance of metal in polymer solution, the additional amount of hydrochloric acid are the amount of the substance of metal in polymer solution
0.1-5.0 times, oxidizing reaction temperature is 30-100 DEG C, and oxidation time is 30-240 minutes；
The chelating of S2, catalyst metals: preparing the chelating liquid that mass concentration is 0.2-5%, and the solute of the chelating liquid is binary carboxylic
Acid, solvent are diethylene glycol monobutyl ether aqueous solution, and the mass concentration of the solvent is 35-85%, and chelating liquid is added to step S1
It is reacted in polymer solution after being aoxidized, chelates the additional amount of liquid in terms of dicarboxylic acids, be metal in polymer solution
1-5 times of the amount of substance, chelatropic reaction temperature are 30-100 DEG C, and the chelatropic reaction time is 30-180 minutes；
S3, liquid separation and precipitating drying: the polymer solution after S2 is chelated is transferred to separatory funnel, stands 60 minutes, solution
It is divided into three layers, divides and go lower two layers, upper solution is the solution for being stripped of catalyst metals；Then by upper solution according to volume
It is injected into dehydrated alcohol than 1:1, after flocculation sedimentation goes out polymer, will dry in precipitating 50 DEG C of vacuum ovens of merging to perseverance
Weight, obtains final polymer.
2. the removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1,
It is characterized in that, in step S1, the oxidizing reaction temperature is 50-70 DEG C, and the oxidation time is 60-120 minutes.
3. the removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1,
It is characterized in that, in step S2, the dicarboxylic acids is decanedioic acid or adipic acid.
4. the removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1,
It is characterized in that, in step S2, the mass concentration of the diethylene glycol monobutyl ether aqueous solution is 50-70%.
5. the removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1,
It is characterized in that, in step S2, the additional amount of the chelating liquid is the amount of the substance of metal in polymer solution in terms of dicarboxylic acids
1.5-2.5 times.
6. the removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1,
It is characterized in that, in step S2, the chelatropic reaction temperature is 50-70 DEG C, and the chelatropic reaction time is 60-120 minutes.
7. the removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1,
It is characterized in that, the unsaturated polymer is the homopolymer of conjugated diene or the copolymer of conjugated diene.
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| CN1067898A (en) * | 1992-07-08 | 1993-01-13 | 北京燕山石油化工公司研究院 | Method for removing residual metal catalyst after polymer hydrogenation |
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