CN109734828A - A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst - Google Patents
A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst Download PDFInfo
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- CN109734828A CN109734828A CN201811591352.3A CN201811591352A CN109734828A CN 109734828 A CN109734828 A CN 109734828A CN 201811591352 A CN201811591352 A CN 201811591352A CN 109734828 A CN109734828 A CN 109734828A
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Abstract
The present invention relates to technical field of polymer, particularly disclose a kind of method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst.The method of the removing unsaturated polymer residure after hydrogenation treatment metallic catalyst, glue is process object after adding hydrogen with the unsaturated polymer containing residual metal catalyst, it is characterized by: lye is added into glue, oxidant is added after mixing carries out oxidation reaction, deionized water washing, stratification, after being agglomerated, being dried are added after reaction, it is anti-to release the metal ion content added in hydrogen post-consumer polymer by metal ion content in test water phase.Operation of the present invention step is simple and easy, can save equipment investment, does not introduce new heavy metal catalyst, solvent recovery is simple, by metal ion content in test water phase, anti-release adds metal ion content remaining in hydrogen post-consumer polymer in 10ppm or so, is suitable for industrialized production.
Description
(1) technical field
The present invention relates to technical field of polymer, in particular to a kind of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst
Method.
(2) background technique
Because containing unsaturated double-bond on polymer chain, chemical property is active by existing styrenic polymer such as SBS, SIS, SBR,
The such environmental effects such as heated, oxygen and ozone are big, and use scope is restricted.Therefore add the side of hydrogen frequently with unsaturated polymer
Method is saturated unsaturated double-bond, so that its environmental stability can be improved, expands application range.
Unsaturated polymer adds the catalyst of hydrogen to be usually heavy metal, and heavy-metal residual can make polymerizate change colour, and influences
The service performance of product.So unsaturated polymer must all remove heavy metal catalyst after adding hydrogen, make polymer it is heat-resisting,
The performances such as oxygen and aging are not influenced by remaining metallic catalyst.
Chinese patent CN102875702A discloses a kind of method for removing metal in polymer, and this method is used in glue
Middle addition machine alkali, such as n-BuLi, phenyl lithium add oxidant, wash after reaction, and finally centrifuge separation, which reaches to remove, removes photoresist
The purpose of metallic residue in liquid.Though it is higher that this method removes metallic residue efficiency in polymer, due to using organic base for alkali
Liquid introduces part metals ion again, leads to raw material investment and de- remainder catalyst higher cost, and additional organic base is to equipment
Requirement it is high.
Chinese patent CN1027172C is disclosed in the glue after a kind of unsaturated polymer adds hydrogen and is removed remainder catalyst
Method, wherein remove metallic catalyst using oxidant and binary acid effect, the solvent of precipitating reagent be more alkyl diol ethers and
The mixture of water, it is high to remainder catalyst removal efficiency in hydrogenated polymers glue using this method, but need to use filtering point
From technology, low separation efficiency is cumbersome, is easy blocking, and industry amplification has certain difficulty.
Disclosed in United States Patent (USP) US4396761 it is a kind of using dilute sulfuric acid processing unsaturated polymer add hydrogen post-consumer polymer
Method separates water phase, then uses water vapour boiling hydrogenated polymers glue, reaches the side of removing residual metal catalyst and solvent
Method obtains polymer.But it is handled with dilute sulfuric acid, new beavy metal impurity may be introduced.
A kind of method for removing heavy metal catalyst in polymer solution is disclosed in United States Patent (USP) US4595749, is used
Oxidant and dicarboxylic acids, fatty alcohol (carbon atom number≤4).Or solvent of the toluene as dicarboxylic acids.Process in this way
Middle discovery, process flow is tediously long, and fatty alcohol is had in recovered solvent, and solvent refining processes require high；When hydrogenated polymers glue
When fluid viscosity is higher, polymer residue heavy metal catalyst is more, and removal effect is bad.
In the method for above-mentioned removing unsaturated polymer catalyst residure after hydrogenation treatment, due to unsaturated polymer plus hydrogen glue
Fluid viscosity is larger, and removing residual heavy metal effect is undesirable；Residual heavy metal catalyst enters acid molten after oxidizing
In liquid, by stratification, make after hydrogenation of polymer that heavy metal ion is extracted in water phase in glue, oily phase-polymerization object enters
Centrifuge, the residual heavy metal ion removing after centrifuge separation is by hydrogenation of polymer in glue is clean, but the throwing of centrifuge
Money and energy consumption are all larger.
(3) summary of the invention
Simple, solvent recovery that in order to compensate for the shortcomings of the prior art, the present invention provides a kind of steps is easy, is suitable for industrial metaplasia
The method of the removing unsaturated polymer residure after hydrogenation treatment metallic catalyst of production.
The present invention is achieved through the following technical solutions:
A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst, with the insatiable hunger containing residual metal catalyst
It is process object with glue after hydrogenation of polymer, it is characterised in that: lye is added into glue, adds oxidation after mixing
Agent carries out oxidation reaction, and deionized water washing is added after reaction, and stratification after being agglomerated, being dried, passes through gold in test water phase
Belong to ion concentration, it is anti-to release the metal ion content added in hydrogen post-consumer polymer.
The present invention is proposed for the first time using lye gap, the polymerization of oxidizing and deionized water washing process unsaturation
Object adds the method for residual metal oxidant in glue after hydrogen.Lye is added in glue after first adding hydrogen to unsaturated polymer, mixes,
Oxidant is added, under the lye of sufficient amount, lye and oxidant reaction produce the stronger peroxide of oxidability, can incite somebody to action
Remaining heavy metal ion is aoxidized and is precipitated, and the purpose of deionized water washing is will to be wrapped in unsaturated polymer to add glue after hydrogen
In part heavy metal ion elution.
More excellent technical solution of the invention are as follows:
The volume ratio of the glue and lye is 1:0.05-5, preferably 1:0.2-2；Lye is sodium hydroxide solution, sodium bicarbonate
One of solution and ammonium hydroxide are a variety of, and preferable ph is the sodium hydroxide solution of 9-10.
The unsaturated polymer is styrenic polymer, and the metal ion of metallic catalyst is in nickel, lithium and aluminium
It is one or more, including the SEBS or SEPS after SBS, SIS and hydrogenation.
The oxidant is hydrogen peroxide, and oxidation dosage is 0.1-5mL/100mL glue, preferable amount 1-2mL/
100mL glue；Oxidizing reaction temperature is 10-100 DEG C, and reaction pressure is normal pressure, speed of agitator 100-1000rpm/min, excellent
Select 200-600rpm/min, reaction time 0.1-5h, preferably 0.2-3h.
The deionized water and the volume ratio of glue are 0.05-5:1, preferably 0. 5-5:1；Stratification 0.1-2h, preferably
0.5-1h。
Unsaturated polymer of the present invention adds glue alkali cleaning, oxidation and deionized water washing after hydrogen that can have mixing same
It is completed in the equipment of function, includes but is not limited to stirred tank, preferably stirred tank in specific embodiment.
Even if method proposed by the present invention, also can be remnants weight in the case where unsaturated polymer adds hydrogen gelatin viscosity big
Metallic catalyst removing, while operating procedure is simple and easy, can save equipment investment, does not introduce new heavy metal catalyst, it is molten
Agent recycling is simple, by metal ion content in test water phase, remaining metal ion content in anti-release plus hydrogen post-consumer polymer
In 10ppm or so, it is suitable for industrialized production.
(4) specific embodiment
To keep goal of the invention of the invention, feature and advantage more obvious and easy to understand, below in conjunction in the embodiment of the present invention
Specific implementation method, the technical solution of the embodiment of the present invention is completely described, in Technology design range of the invention
It is interior, can be with various simple variants of the technical solution of the present invention are made, this simple modification belongs to protection model of the invention
It encloses.
In addition it needs to propose to illustrate, be only a part of the embodiment of the present invention in embodiments described below, rather than
Whole embodiments.Based on embodiment in the present invention, those skilled in the art are not making creative work premise
Under other all embodiments obtained, belong to the scope protected of the present invention.
Preparation example: unsaturated polymer and the preparation for adding hydrogen glue
Preparation example 1:
In 3L stainless steel polymeric kettle, using n-BuLi as initiator, the mixed liquor of hexamethylene and n-hexane is solvent, styrene
It is polymerized monomer with butadiene, synthesizes triblock copolymer by structure regulator of oxygen-containing polar solvent.Obtained unsaturation
Polymer, molecular weight are 100,000,1,2-% 40.B-S-B block copolymer is transferred to and is added in hydrogen kettle
It is spare.
Preparation example 2:
In 3L stainless steel polymeric kettle, using n-BuLi as initiator, the mixed liquor of hexamethylene and n-hexane is solvent, styrene
It is polymerized monomer with butadiene, synthesizes triblock copolymer by structure regulator of oxygen-containing polar solvent.Obtained unsaturation
Polymerizate, molecular weight are 200,000,1,2-% 40.B-S-B block copolymer is transferred to and adds hydrogen kettle
In it is spare.
Preparation example 3:
Unsaturated polymer adds the catalyst of hydrogen mainly to have nickel system and luxuriant titanium catalyst system.Perseverance using nickel catalyst at 55 DEG C
It is aged 30min in tepidarium to be made, catalyst amount is 0.07g/100g polymer.Take styrene-fourth two of preparation example 1/2
Alkene-styrene block copolymer is to add hydrogen-based plinth glue, and the catalyst of ageing is transferred to 2L and adds hydrogen kettle, reaction temperature 70
DEG C, hydrogenation pressure 2Mpa, speed of agitator 800-1000rpm/min react 2h.It is measured using iodimetric titration and adds hydrogen post-consumer polymer
Degree of hydrogenation be 97%.
Embodiment 1:
Glue after unsaturated polymer plus hydrogen is transferred to stirred tank, carries out the de- of unsaturated polymer catalyst residure after hydrogenation treatment
It removes.Treatment conditions are as follows: glue 500ml is transferred to stirred tank after taking unsaturated polymer to add hydrogen, and stirred tank revolving speed is 400rpm/
Min, stirred tank temperature are 70 DEG C, and lye 500ml is added to stirred tank, add 10ml30% hydrogen peroxide and carry out oxidation reaction,
After 30min, 250ml deionized water is added and is washed, stops to stir after 20min, stratification.Upper layer unsaturated polymer adds hydrogen
Glue is agglomerated, is dried afterwards, and lower aqueous solution surveys the catalyst heavy metal ion in being soluble in the aqueous phase using plasma emission spectrum
Concentration, anti-nickel of extrapolating in dry back end hydrogenation post-consumer polymer is 8PPm, aluminium 5PPm, lithium 1PPm.
Embodiment 2:
Glue after unsaturated polymer plus hydrogen is transferred to stirred tank, carries out the de- of unsaturated polymer catalyst residure after hydrogenation treatment
It removes.Treatment conditions are as follows: glue 500ml is transferred to stirred tank after taking unsaturated polymer to add hydrogen, and stirred tank revolving speed is 400rpm/
Min, stirred tank temperature are 70 DEG C, and lye 500ml is added to stirred tank, add 8ml30% hydrogen peroxide and carry out oxidation reaction,
After 30min, 250ml deionized water is added and is washed, stops to stir after 20min, stratification.Upper layer unsaturated polymer adds hydrogen
Glue is agglomerated, is dried afterwards, and lower aqueous solution surveys the catalyst heavy metal ion in being soluble in the aqueous phase using plasma emission spectrum
Concentration, anti-nickel of extrapolating in dry back end hydrogenation post-consumer polymer is 10PPm, aluminium 4PPm, lithium 2PPm.
Embodiment 3:
Glue after unsaturated polymer plus hydrogen is transferred to stirred tank, carries out the de- of unsaturated polymer catalyst residure after hydrogenation treatment
It removes.Treatment conditions are as follows: glue 500ml is transferred to stirred tank after taking unsaturated polymer to add hydrogen, and stirred tank revolving speed is 400rpm/
Min, stirred tank temperature are 70 DEG C, and lye 500ml is added to stirred tank, add 10ml30% hydrogen peroxide and carry out oxidation reaction,
After 30min, 500ml deionized water is added and is washed, stops to stir after washing, stratification.Upper layer unsaturated polymer adds hydrogen
Glue is agglomerated, is dried afterwards, and lower aqueous solution surveys the catalyst heavy metal ion in being soluble in the aqueous phase using plasma emission spectrum
Concentration, anti-nickel of extrapolating in dry back end hydrogenation post-consumer polymer is 5PPm, aluminium 5PPm, lithium 1PPm.
Embodiment 4:
Glue after unsaturated polymer plus hydrogen is transferred to stirred tank, carries out the de- of unsaturated polymer catalyst residure after hydrogenation treatment
It removes.Treatment conditions are as follows: glue 500ml is transferred to stirred tank after taking unsaturated polymer to add hydrogen, and stirred tank revolving speed is 400rpm/
Min, stirred tank temperature are 70 DEG C, and lye 500ml is added to stirred tank, add 10ml30% hydrogen peroxide and carry out oxidation reaction,
After 30min, 250ml deionized water is added and is washed, stops to stir after 20min, stratification.Upper layer unsaturated polymer adds hydrogen
Glue is agglomerated, is dried afterwards, and lower aqueous solution surveys the catalyst heavy metal ion in being soluble in the aqueous phase using plasma emission spectrum
Concentration, anti-nickel of extrapolating in dry back end hydrogenation post-consumer polymer is 10PPm, aluminium 7PPm, lithium 5PPm.
Embodiment 5:
Glue after unsaturated polymer plus hydrogen is transferred to stirred tank, carries out the de- of unsaturated polymer catalyst residure after hydrogenation treatment
It removes.Treatment conditions are as follows: glue 500ml is transferred to stirred tank after taking unsaturated polymer to add hydrogen, and stirred tank revolving speed is 400rpm/
Min, stirred tank temperature are 70 DEG C, and lye 500ml is added to stirred tank, add 10ml30% hydrogen peroxide and carry out oxidation reaction,
After 30min, 250ml deionized water is added and is washed, stops to stir after 20min, stratification.Upper layer unsaturated polymer adds hydrogen
Glue is agglomerated, is dried afterwards, and lower aqueous solution surveys the catalyst heavy metal ion in being soluble in the aqueous phase using plasma emission spectrum
Concentration, anti-nickel of extrapolating in dry back end hydrogenation post-consumer polymer is 10PPm, aluminium 6PPm, lithium 2PPm.
Embodiment 6:
Glue after unsaturated polymer plus hydrogen is transferred to stirred tank, carries out the de- of unsaturated polymer catalyst residure after hydrogenation treatment
It removes.Treatment conditions are as follows: glue 500ml is transferred to stirred tank after taking unsaturated polymer to add hydrogen, and stirred tank revolving speed is 400rpm/
Min, stirred tank temperature are 60 DEG C, and lye 500ml is added to stirred tank, add 10ml30% hydrogen peroxide and carry out oxidation reaction,
After 30min, 250ml deionized water is added and is washed, stops to stir after 20min, stratification.After upper layer insatiable hunger hydrogenation of polymer
Glue is agglomerated, is dried, and it is dense that lower aqueous solution uses plasma emission spectrum to survey the catalyst heavy metal ion in being soluble in the aqueous phase
Degree, anti-nickel of extrapolating in dry back end hydrogenation post-consumer polymer is 6PPm, aluminium 8PPm, lithium 2PPm.
Particularly, the method for removing unsaturated polymerization catalyst residure after hydrogenation treatment is carried out using method of the invention, not only
Equipment investment expense can be greatlyd save, and does not introduce new beavy metal impurity and solvent, it is important that unsaturated polymer
Remaining catalyst metal ion content is in 10ppm or so after adding hydrogen.
Claims (9)
1. it is a kind of remove unsaturated polymer residure after hydrogenation treatment metallic catalyst method, with containing residual metal catalyst not
Saturated polymer adds glue after hydrogen to be process object, it is characterised in that: lye is added into glue, adds oxygen after mixing
Agent carries out oxidation reaction, and deionized water washing, stratification, after being agglomerated, being dried, by test water phase are added after reaction
Metal ion content, it is anti-to release the metal ion content added in hydrogen post-consumer polymer.
2. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 1, feature exist
In: the volume ratio of the glue and lye is 1:0.05-5, and lye is in sodium hydroxide solution, sodium bicarbonate solution and ammonium hydroxide
It is one or more.
3. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 1, feature exist
In: the unsaturated polymer be styrenic polymer, the metal ion of metallic catalyst be one of nickel, lithium and aluminium or
It is a variety of.
4. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 1, feature exist
In: the oxidant is hydrogen peroxide, and oxidation dosage is 0.1-5mL/100mL glue；Oxidizing reaction temperature is 10-100 DEG C, instead
Answering pressure is normal pressure, speed of agitator 100-1000rpm/min, reaction time 0.1-5h.
5. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 1, feature exist
In: the deionized water and the volume ratio of glue be 0.05-5:1, stratification 0.1-2h.
6. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 2, feature exist
In: the volume ratio of the glue and lye is 1:0.2-2, and lye is the sodium hydroxide solution that pH value is 9-10.
7. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 3, feature exist
In: the unsaturated polymer is SBS, SIS, SEBS or SEPS.
8. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 4, feature exist
In: the oxidation dosage of the oxidant is 1-2mL/100mL glue；The speed of agitator of oxidation reaction is 200-600rpm/min,
Reaction time is 0.2-3h.
9. the method for removing unsaturated polymer residure after hydrogenation treatment metallic catalyst according to claim 5, feature exist
In: the deionized water and the volume ratio of glue be 0. 5-5:1, stratification 0.5-1h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912796A (en) * | 2020-07-08 | 2022-01-11 | 沈阳化工研究院有限公司 | Method for removing residual catalyst in unsaturated polymer hydrogenation reaction |
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Application publication date: 20190510 |